JPH11255866A - Epoxy resin composition for civil engineering and construction, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition with low viscosity and low mutagenicity by incorporating an epoxy resin prepared by reacting allylated bisphenol compounds with epihalohydrin compounds. SOLUTION: There is provided a composition comprising 100 pts.wt. of an epoxy resin mixture comprising at least 30 wt.% of an epoxy resin represented by formula I and other epoxy resins, 1-10,000 pts.wt. of a curing agent selected from amine compounds, acid anhydride compounds, amide compounds and phenolic compounds, further, 0.01-10 pts.wt. of a curing accelerator such as 2- methylimidazole and the like, a filler, a silane coupling agent and the like. The epoxy resin represented by formula I is obtained by reacting a compound represented by formula II, obtained by allylation of a bisphenol compound, with an epihalohydrin compound in the presence of an alkali metal hydroxide catalyst. In the formulae, n represents 0-1; X represents a single bond, a 1-7C hydrocarbon, S, O, -SO- and the like; Y represents H or 1-4C alkyl; and R represents l-6C alkyl, aryl or allyl (which forms 13-50% of the whole).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition used for civil engineering and construction, and a cured product thereof.

[0002]

2. Description of the Related Art Diglycidyl bisphenols which are liquid at room temperature are excellent in workability due to their low viscosity, and in particular, glycidylated products of bisphenol A and bisphenol F are inexpensive, so they are repair materials for civil engineering and construction. Various forms (paints, sealing materials, adhesives, FRP, etc.) for civil engineering and construction materials, including pavement materials, civil engineering and construction adhesives, civil construction and rust prevention paints, and building interior and exterior materials
Resin, etc.) and are used in large quantities.

[0003]

However, since epoxy resin compositions for civil engineering and construction are often used at construction sites, the viscosity and reactivity change due to changes in temperature, so that the workability, pot life, There are operational problems that the curing time varies depending on the season, and resistance to weather conditions such as wind, rain and sunlight. In recent years, environmental issues have been emphasized in recent years, and it is undeniable that there is a possibility that a resin composition will flow out due to an accident or a mistake in a workplace of civil engineering or construction, and that the surrounding living body will be affected by mutation or the like. Furthermore, workers usually wear protective equipment, but this also means that the resin composition does not directly adhere to skin etc. due to accidents, mistakes, or non-wearing of protective equipment due to annoyance in summer. In addition, if an organic solvent is used, it is gasified and released into the environment, causing not only harm to workers but also environmental destruction. Therefore, there is a need for a resin composition using an epoxy resin having a lower viscosity and a lower mutagenicity (eg, negative in the Ames test) than an epoxy resin that is currently frequently used.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on a solution to the above-mentioned problem and completed the present invention. That is, the present invention provides the following equation (1):

[0005]

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(Wherein, n represents an average value and is a real number of 0 to 1. X is each independently a single bond, 1 to 7 carbon atoms.
A hydrocarbon group or a sulfur atom, an oxygen atom, -SO-,-
SO ₂ —, —CO—, —CO ₂ — or —Si (C
H ₃ ) _2- . Y each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Multiple R
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an allyl group;
0% is an allyl group. And (2) the epoxy resin composition for civil engineering and construction according to the above (1), which does not contain an organic solvent, and (3) the epoxy resin composition for civil engineering and construction which does not contain an organic solvent. (2) A cured product obtained by curing the epoxy resin composition described in (2).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin used in the present invention has the following formula (2)

[0008]

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(Wherein X and R have the same meanings as in formula (1)) and an epihalohydrin can be reacted (epoxidation reaction).

The compound of the formula (2) can be obtained by reacting various bisphenols with allyl halide, subjecting them to allyl etherification, and then subjecting the allyl group to Claisen rearrangement. The starting materials bisphenols, monoallylbisphenols, diallylbisphenols , Triallyl bisphenols and tetraallyl bisphenols alone or in a mixture, wherein the number of allyl groups in all R is 13 to 50%. Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol AD, biphenol, cyclohexylidenebisphenol, bisphenol S, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxy Phenyl) methanone, 4,4 ′-(dimethylsilylene) bisphenol,
4,4'-oxybisphenol and the like. As the compound of the formula (2), not only a compound obtained by allylating bisphenols alone as described above but also a compound obtained by allylating two or more kinds in the same system may be used. These compounds may be used as a mixture of two or more. Further, the compound of the formula (2) can also be obtained as a heavy (condensed) compound of a phenol having an allyl group with various aldehydes or ketones, various diene compounds, or various aromatic dimethylol compounds.

Specific examples of the epihalohydrins that can be used in the epoxidation reaction include epichlorohydrin, β-methylepichlorohydrin, epibromohydrin, β-methylepibromohydrin, epiiodohydrin, β-ethylepichlorohydrin and the like. But
Epichlorohydrin or epibromohydrin, which is industrially available and inexpensive, is preferred.

The reaction is carried out, for example, by reacting a mixture of the compound of the formula (2) and epihalohydrins with sodium hydroxide as a catalyst,
While adding the solid of alkali metal hydroxide such as potassium hydroxide all at once or gradually adding the solid, the solution is added at 0.2 to 120 ° C. at 0.degree.
Incubate for 5 to 10 hours. At this time, an aqueous solution of the alkali metal hydroxide may be used. In such a case, the alkali metal hydroxide is continuously added, and water and epihalohydrin are continuously added to the reaction mixture under reduced pressure or normal pressure. The epihalohydrins may be continuously distilled back to the reaction mixture by distilling off the components and separating water to remove water (the solid alkali metal hydroxide may also be dehydrated under reduced pressure).

In the above reaction, the amount of the epihalohydrin used per 1 equivalent of the hydroxyl group of the compound of the formula (2) increases as the number of repeating units (n) decreases and the viscosity becomes lower. If considered, it is usually 1.0 to 20 mol, preferably 2.0 to 15 mol, more preferably 3.
0 to 10 mol. The amount of the alkali metal hydroxide to be used is generally 0.5 to 1 equivalent of the hydroxyl group of the compound of the formula (2).
1.5 mol, preferably 0.7 to 1.2 mol.

Further, as the compound of the formula (2), a compound in which an allyl group is substituted at the ortho position of a hydroxyl group is particularly preferred. In this case, the reactivity between the hydroxyl group and epihalohydrin
Bad compared to the hydroxyl groups of ordinary phenols and cresols. Accordingly, the reaction is preferably carried out using an aprotic polar solvent or a solvent having a catalytic ability such as alcohols. Specific examples of aprotic polar solvents that can be used include:
Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and 1,4-dioxane. The amount of the aprotic polar solvent to be used is generally 5-200% by weight, preferably 10-150% by weight, based on the weight of epihalohydrins. Specific examples of alcohols that can be used include methanol, ethanol, methoxypropanol, and the like. The amount of the alcohol used is usually 5 to 100% by weight, preferably 5 to 50% by weight, based on the weight of the epihalohydrin.

In the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride can be used as a catalyst. In this case, the amount of the quaternary ammonium salt used is usually 0.001 to 1 equivalent of the hydroxyl group of the compound of the formula (2).
To 0.2 mol, preferably 0.05 to 0.1 mol. These may be used in combination with the above solvents.

Usually, these reaction products are used under washing with or without washing under heating and reduced pressure to obtain an excess of epihalohydrins,
After removing the used solvent and the like, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is added thereto. Epoxy resin with a small amount of water. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.2 mol per 1 equivalent of the hydroxyl group of the compound of the formula (2),
Preferably it is 0.05 to 0.15 mol. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours. After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, or the like, and the solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone is distilled off under reduced pressure under heating to obtain the epoxy resin used in the present invention.

The epoxy resin thus obtained is
Since it has low viscosity and low crystallinity, it can be used as a diluent for diluting a resin having a high viscosity or a solid resin, or for changing the viscosity depending on the application temperature. In addition, it is also possible to cure using a compound having a group that reacts with an allyl group in addition to a usual curing agent for an epoxy resin. A cured resin having a higher crosslinking density than that of the resin is obtained.

Next, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the present invention, the formula (1)
Can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the formula (1) in the total epoxy resin is preferably at least 30% by weight, particularly preferably at least 40% by weight.

Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the formula (1) include bisphenols and phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.). Polycondensates with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylol,
Biphenols, glycidyl ether-based epoxy resin glycidylated alcohols, etc., alicyclic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin brominated epoxy resin and the like, but are not limited thereto Those having low mutagenicity are preferred. These may be used alone or in combination of two or more.

[0020] In a preferred embodiment of the epoxy resin composition of the present invention, a curing agent is contained. As a curing agent, amine compounds, acid anhydride compounds, amide compounds,
Phenol compounds and the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and trianhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, or bisphenols, phenols (phenol, alkyl Polycondensates of substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, phenols and various diene compounds , Polycondensates of phenols with aromatic dimethylol, biphenols and modified products thereof, polyhydric phenol compounds such as the compound of the formula (2) and allylic products of the phenol compounds, imidazole, BF ₃ −
Examples include an amine complex and a guanidine derivative. Also,
In addition to the above, bismaleimide diphenylmethane, bismaleimide ethane, bismaleimide hexane, bismaleimide benzene, phenylmaleimide, a compound having a maleimide group such as methylmaleimide, a compound having a cyanate ester group, and the like, but also an epoxy group or an allyl group Compounds other than those described above may be used as long as they have a group that reacts with, but compounds having low mutagenicity are preferred.
The curing agent is used in an amount of 1 to 10000 parts by weight based on 100 parts by weight of the total epoxy resin.

When the above curing agent is used, a curing accelerator may be used in combination. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol,
1,8-diaza-bicyclo (5,4,0) undecene-
Tertiary amines such as 7, phosphines such as triphenylphosphine, and organometallic compounds such as tin octylate, zinc naphthenate and cobalt naphthenate, but are not limited thereto, and are not mutagenic. Are preferred. The curing accelerator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total weight of the epoxy resin and the curing agent.

Further, the epoxy resin composition of the present invention may contain silica, alumina, talc, aluminum hydroxide, calcium silicate, tar, asphalt,
Fillers such as glass flakes and silane coupling agents, release agents, pigments, thermoplastic resins, various compounding agents such as curable organic resins other than those described above can be added, but substances having low mutagenicity may be added. preferable.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, preferably a curing agent, and, if necessary, a curing accelerator, a filler, and a compounding agent are sufficiently mixed by using an extruder, a kneader, or the like, if necessary, until the mixture becomes uniform. The epoxy resin composition of the present invention is obtained, and the epoxy resin composition is applied to a substrate as a paint or an adhesive or injected into cracks in concrete, and then cured. Curing is
Depending on the reactivity of the curing agent and curing accelerator in the composition,
Heating may be necessary, and curing is possible even at the temperature of the construction site.

The epoxy resin composition of the present invention preferably does not contain an organic solvent in order to protect the working environment. However, the epoxy resin of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone or methyl isobutyl ketone. A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and heating and drying is coated with a structure such as concrete, and then cured. it can. The physical properties of the cured product after being applied as described above have low hygroscopicity due to the main component of the allyl-based epoxy resin, and can reduce performance deterioration due to moisture absorption.

[0025]

The present invention will be described below in more detail with reference to production examples and examples. Note that the present invention is not limited to these examples. In addition, the physical properties of the epoxy resin were measured by the following methods. Epoxy equivalent: measured by a method according to JIS K-7236. Viscosity: Measured at 25 ° C. with an E-type rotational viscometer.

Production Example 1 A reactor was charged with 154 parts by weight of diallyl bisphenol A, 400 parts by weight of epichlorohydrin (ECH, the same applies hereinafter), and 40 parts by weight of methanol.
While maintaining the temperature at 5 ° C., 41 parts by weight of flaky sodium hydroxide was gradually added over 2 hours. After the completion of the addition of sodium hydroxide, the reaction was further performed at 75 ° C. for 2 hours. Next, washing with water is repeated to remove the produced salt and methanol, and then excess ECH is distilled off from the oil layer under heating and reduced pressure, and 400 parts by weight of methyl isobutyl ketone (MIBK, the same applies hereinafter) is added to the residue and dissolved. did. This MIBK solution was added to 70
After heating to 10 ° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. Thereafter, water washing was repeated until the washing liquid became neutral. Then, MIBK was distilled off from the oil layer under heating and reduced pressure to obtain an epoxy resin (E
1) 198 parts by weight were obtained. The obtained epoxy resin (E
The epoxy equivalent of 1) is 225 g / eq, and the viscosity is 2000
It was centipoise.

Production Example 2 The same operation as in Production Example 1 was carried out except that diallyl bisphenol A was changed to 140 parts by weight of diallyl bisphenol F, to obtain 187 parts by weight of an epoxy resin (E2). The epoxy equivalent of the epoxy resin (E2) is 21.
0 g / eq and the viscosity was 1000 centipoise.

Examples 1-2, Comparative Example 1 The epoxy resins (E1) and (E2) obtained in Production Examples 1 and 2, Epicoat 828 (R1) (Epoxy equivalent of Yuka Shell Epoxy Co., Ltd.) as a comparative example 185g / e
Using q), 63 parts by weight of a curing agent 4,4′-methylenebis (2,6-dimethylaniline) is blended with respect to one epoxy equivalent of the epoxy resin, and the mixture is uniformly dissolved and poured into a mold.
A cured product was obtained by curing at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1. The physical properties of the cured products were measured by the following methods. Water absorption: Weight increase rate (%) after boiling a disc-shaped test piece having a diameter of 5 cm and a thickness of 4 mm in water at 100 ° C. for 24 hours Copper foil peel strength: 180 ° peel test Measurement temperature; 30 ° C. Pulling speed: 200 mm / Min Copper foil; JTC foil 70 μm manufactured by Nikko Gould Co., Ltd.

[0030]

Table 1 Example Comparative Example 12 21 Epoxy resin E1 E2 R1 Water absorption (%) 1.0 1.1 1.3 Copper foil peel strength (Kg / cm) 4.3 4.5 4.0

[0031]

The epoxy resin used in the epoxy resin composition for civil and architectural use according to the present invention has low viscosity and extremely low crystallinity at low temperature. Reduced or no use,
The composition has such characteristics that crystallization of the composition hardly occurs even at a low temperature. Further, the cured product is excellent in adhesiveness to an adherend, low hygroscopicity, and the like. Furthermore, since the epoxy resin has low mutagenicity, the epoxy resin composition composed of other compounds and substances having low mutagenicity also has a detrimental effect on the living body, environment, and workers near the construction site. Can be reduced.

Claims (3)

[Claims] (1) Formula (1) (Where n represents an average value and is a real number from 0 to 1. X
Are each independently a single bond, a hydrocarbon group, or a sulfur atom 1 to 7 carbon atoms, an oxygen _{atom, -SO -, - SO 2 -} ,
-CO -, - CO ₂ - or -Si (CH _{3) 2} - shows a. Y is each independently a hydrogen atom or carbon number 1 to
4 represents an alkyl group. A plurality of Rs each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an allyl group, and 13 to 50% of the whole is an allyl group. An epoxy resin composition for civil engineering and construction containing the epoxy resin represented by the formula (1). 2. The epoxy resin composition for civil and architectural use according to claim 1, which does not contain an organic solvent. 3. A cured product obtained by curing the epoxy resin composition according to claim 1 or 2.