JP2006083306A - Diglycidyl ether, curable composition and cured product - Google Patents

Abstract

で示されるジグリシジルエーテル［以下、ジグリシジルエーテル（１）と称する。］、
［２］ ジグリシジルエーテル（１）、エポキシ樹脂［ａ］および硬化剤［ｂ］を含有する硬化性組成物、
［３］ さらに下記式（２）
【化２】

で示されるジグリシジルエーテルを含有する上記［２］の硬化性組成物、および
［４］ ［２］または［３］の硬化性組成物を硬化してなる硬化物。
【選択図】なしDisclosed is a diglycidyl ether that is useful as a resin modifier, a crosslinking agent, a paint, a coating agent, an ink, a pharmaceutical, an adhesive, a binder, a paper / fiber modifier, an epoxy resin reactive diluent, and the like. thing.
[1] The following formula (1)
[Chemical 1]

Diglycidyl ether [hereinafter referred to as diglycidyl ether (1). ],
[2] A curable composition containing diglycidyl ether (1), epoxy resin [a] and curing agent [b],
[3] Further, the following formula (2)
[Chemical 2]

The curable composition of the above [2] containing the diglycidyl ether represented by [4] and a cured product obtained by curing the curable composition of [4] [2] or [3].
[Selection figure] None

Description

  The present invention provides [i] the following formula (1)

Diglycidyl ether [hereinafter abbreviated as diglycidyl ether (1). ],
[Ii] a curable composition containing diglycidyl ether (1), an epoxy resin [a] and a curing agent [b],
[Iii] Furthermore, following formula (2)

Diglycidyl ether [hereinafter abbreviated as diglycidyl ether (2). ] [Ii] The curable composition of [ii] and [iv] [ii] or [iii] The curable composition obtained by curing.
The diglycidyl ether (1) obtained by the present invention is a resin modifier, a crosslinking agent, a paint, a coating agent, an ink, a pharmaceutical, an adhesive, a binder, a paper / fiber modifier, and particularly a reactivity of an epoxy resin. Useful as a diluent.

  Epoxy resins have excellent adhesion to various materials such as metal, glass, and plastic, as well as high heat resistance, chemical resistance, electrical insulation, and low cure shrinkage. It is used for various applications such as ink and semiconductor encapsulant. However, epoxy resins generally have a problem of high viscosity and poor workability. In order to improve this, an epoxy resin is usually mixed with a reactive diluent to form a composition, and the viscosity of the composition is lowered while maintaining curability. As such reactive diluents, conventionally, monoglycidyl ethers such as methyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether; 1,6-hexanediol diglycidylated product (Poly) glycidyl ethers such as (poly) alkylene glycol diglycidyl compounds such as diglycidyl compounds of 2-butyl-2-ethyl-1,3-propanediol, diglycidyl compounds of neopentyl glycol, diglycidyl compounds of diethylene glycol; Glycidyl esters such as glycidyl, diglycidyl dimer, and diglycidyl terephthalate are known (see, for example, Non-Patent Document 1).

“Review Epoxy Resin Basics II”, Epoxy Resin Technology Association, November 19, 2003, p. 45-54

When the above-mentioned conventional reactive diluent is added to the epoxy resin, the viscosity is lowered and the workability is improved, but depending on the type and amount of the reactive diluent, the composition comprising the epoxy resin and the reactive diluent Problems such as a decrease in physical properties such as a decrease in mechanical strength of a cured product obtained by curing the product and an increase in water absorption occur. Therefore, development of the reactive diluent which can obtain the hardened | cured material which is excellent in a mechanical characteristic and has a low water absorption is desired.
The present invention solves the above-mentioned problems, and in particular, a novel glycidyl ether useful as a reactive diluent for an epoxy resin, a curable composition containing the glycidyl ether, and a cured product obtained by curing the curable composition The purpose is to provide.

According to the present invention, the above problem is
[I] diglycidyl ether (1),
[Ii] a curable composition containing diglycidyl ether (1), an epoxy resin [a] and a curing agent [b],
[Iii] Provided is a curable composition of the above [ii] that further contains diglycidyl ether (2), and a cured product obtained by curing the curable composition of [iv] [ii] or [iii]. Is achieved.

  According to the present invention, it is useful as a resin diluent, a crosslinking agent, a paint, a coating agent, an ink, a pharmaceutical, an adhesive, a binder, a paper / fiber modifier, etc., particularly as a reactive diluent for an epoxy resin. A novel glycidyl ether that provides a cured product having excellent mechanical properties and low water absorption is provided. And the curable composition containing this glycidyl ether, an epoxy resin, and a hardening | curing agent, and the hardened | cured material formed by hardening | curing this curable composition are useful as a coating material, an adhesive agent, ink, a semiconductor sealing material, etc.

  The production method of the diglycidyl ether (1) of the present invention is not particularly limited. For example, 2-methyl-1,8-octanediol is converted into epihalohydrin in the presence of a basic substance and, if necessary, a phase transfer catalyst and a solvent. (Hereinafter, this reaction is referred to as “reaction 1”). Hereinafter, the reaction 1 will be described in detail as an example of a method for producing the diglycidyl ether (1).

  Examples of epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Although there is no restriction | limiting in particular in the usage-amount of epihalohydrin, Usually, it is preferable that it is the range of 0.5-20 times mole with respect to 2-methyl- 1,8-octanediol, and from a viewpoint of a yield and volume efficiency. Is more preferably in the range of 1 to 10 moles.

  Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride. The amount of the basic substance used is preferably in the range of 0.5 to 20 times mol, more preferably in the range of 1 to 10 times mol with respect to 2-methyl-1,8-octanediol. You may use a basic substance in the state of aqueous solution. In that case, it is preferable that the usage-amount of water is the range of 0.2-10 times mass with respect to this basic substance, and it is more preferable that it is the range of 0.5-4 times mass.

  When an alkali metal hydroxide is used as the basic substance, or when the basic substance is used as an aqueous solution for the reaction, the reaction may be performed while removing water (including water by-produced as the reaction proceeds). . As a method for removing water, for example, a method in which a dehydrating agent such as sodium sulfate, magnesium sulfate or molecular sieve coexists in the reaction system, an epihalohydrin used as a raw material, or an azeotropic distillation with such a solvent when a solvent is used. And a method of removing water out of the reaction system.

  In Reaction 1, when an aqueous solution such as an aqueous sodium hydroxide solution is used as the basic substance, it is usually preferable to use a phase transfer catalyst. There are no particular restrictions on the type of phase transfer catalyst, but for example, quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, cetyltrimethylammonium chloride, benzyltriethylammonium chloride; tetrabutylphosphonium chloride And phosphonium salts such as crown ethers such as 15-crown-5 and 18-crown-6. When a phase transfer catalyst is used, the amount used is usually preferably in the range of 0.001 to 0.5 moles relative to 2-methyl-1,8-octanediol, 0.01 to The range of 0.2 mole is more preferable.

  Reaction 1 can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; saturated aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether, Examples include ethers such as diethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. These may be used individually by 1 type, and may use 2 or more types together. When a solvent is used, the amount used is not particularly limited, but it is usually preferably in the range of 0.01 to 20 times the mass with respect to 2-methyl-1,8-octanediol. More preferably, it is in the range of 10 to 10 times the mass. In reaction 1, diglycidyl ether (1) can be produced efficiently even when carried out in the absence of a solvent, which is particularly preferable from the viewpoint of volumetric efficiency.

  The reaction temperature of reaction 1 is usually preferably in the range of -30 to 150 ° C, more preferably in the range of -10 to 120 ° C. If it is less than -30 degreeC, it will become the tendency for reaction rate to fall extremely. On the other hand, when it exceeds 150 ° C., for example, side reactions such as polymerization tend to occur, and the yield of diglycidyl ether (1) tends to decrease. The reaction time is usually preferably in the range of 10 minutes to 15 hours, and more preferably in the range of 10 minutes to 10 hours from the viewpoint of suppressing side reactions.

  Reaction 1 is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of safety. The reaction can be carried out under reduced pressure, atmospheric pressure, or increased pressure.

  In the reaction 1, for example, an aqueous solution of a basic substance, 2-methyl-1,8-octanediol, epihalohydrin and, if necessary, a solvent and a phase transfer catalyst are charged at one time or dividedly, and an epihalohydrin is prepared. Alternatively, the reaction can be carried out at a predetermined temperature and a predetermined pressure for a predetermined time while removing water out of the system by azeotropic distillation with a solvent.

  After completion of the reaction, the solid residue is removed from the reaction solution by filtration. If necessary, the organic layer is concentrated after washing with water, saturated saline, etc., and further a simple organic compound such as distillation or column chromatography is used. Highly pure diglycidyl ether (1) can be obtained by carrying out an operation usually used in separation / purification.

  The diglycidyl ether (2) can be produced in the same manner as in the above reaction 1 using 1,9-nonanediol as a raw material.

  In addition, 2-methyl-1,8-octanediol which is a raw material of diglycidyl ether (1) and 1,9-nonanediol which is a raw material of diglycidyl ether (2) are obtained by hydroformylation of 7-octenal. 2-Methyl-1,8-octane dial and 1,9-nonane dial can be easily produced by hydrogenation in the presence of a hydrogenation catalyst such as Raney nickel and in a hydrogen atmosphere.

Next, the curable composition containing the diglycidyl ether (1) of the present invention, the epoxy resin [a] and the curing agent [b] will be described in detail.
The diglycidyl ether (1) of the present invention can be used as a reactive diluent. For example, after the diglycidyl ether (1) is mixed with the epoxy resin [a] to reduce the viscosity, the curing agent [b] is further added, and if necessary, other reactive diluents [c] and / or Alternatively, an additive [d] or the like is added to obtain a curable composition (a composition that is heated or cured by irradiating active energy rays), and the obtained curable composition is heated or activated energy. A cured product can be obtained by irradiating a line. Hereinafter, a mixture obtained by adding diglycidyl ether (1), epoxy resin [a], and other reactive diluent [c] as necessary may be referred to as “diluted resin”.
When obtaining such a curable composition, there is no restriction | limiting in particular in the usage-amount of diglycidyl ether (1), Usually, it is the range of 0.1-50 mass% with respect to all the components in a curable composition. Is more preferable, it is more preferable that it is the range of 0.5-40 mass%, and it is still more preferable that it is the range of 1-30 mass%.

  There is no restriction | limiting in particular as an epoxy resin [a], A well-known high viscosity epoxy compound or an epoxy resin can be used, As a high viscosity epoxy compound, it is a compound whose viscosity is higher than the diglycidyl ether (1) of this invention. For example, cycloaliphatic esters such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate; diglycidyl phthalate, diterephthalate Glycidyl esters such as glycidyl ester and glycidyl hexahydrophthalate; amine-based glycidyl such as tetraglycidyl diaminodiphenylmethane, diglycidyl toluidine, tetraglycidyl metaxylylene diamine, triglycidyl isocyanurate Such compounds. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, Examples thereof include glycidyl ether type epoxy resins such as tetrafunctional naphthalene type epoxy resins and phenol / biphenylene type epoxy resins. These epoxy resins [a] may be used individually by 1 type, and may use 2 or more types together. It is preferable that the usage-amount of epoxy resin [a] is the range of 5-95 mass% with respect to the curable composition whole quantity.

  Examples of the curing agent [b] include a curing agent that is cured by heat and a curing agent that is cured by irradiation with active energy rays such as ultraviolet rays.

Examples of the curing agent that is cured by heat include amine curing agents, acid anhydride curing agents, phenol curing agents, dicyandiamide, and imidazoles.
Examples of amine-based curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, metaxylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro. [5.5] Aliphatic amines such as undecane; Cycloaliphatic amines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornanediamine, 1,2-diaminocyclohexane; Aromatic amines such as diphenylmethane and metaphenylenediamine; heterocyclic amines such as N-aminoethylpiperazine and the like.
Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, dodecenyl succinic anhydride, chlorendic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
4-methyltetrahydrophthalic anhydride, 5-methylnorbornane-2,3-dicarboxylic anhydride, 5-methyl-5-norbornene-2,3-dicarboxylic anhydride, 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
Examples of the phenolic curing agent include phenol novolak, triphenylmethane novolak, xylylene novolak, and biphenyl novolak.
Examples of imidazoles include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenylimidazoline, and the like.

  On the other hand, examples of the curing agent that is cured by irradiation with active energy rays such as ultraviolet rays include compounds represented by the following chemical formulas such as aromatic sulfonium salts and aromatic iodonium salts.

(In the formula, R ^{1 to} R ⁵ may each independently have hydrogen, an alkyl group optionally having a hydroxyl group having 1 to 18 carbon atoms, or a hydroxyl group having 1 to 18 carbon atoms. Represents an alkoxyl group, M represents boron, phosphorus, arsenic or antimony, X represents a halogen or a pentafluorophenyl group, k represents a valence of M, specifically, when M is boron, k Is 3, and when M is phosphorus, arsenic or antimony, k is 5.)

  These curing agents [b] may be used alone or in combination of two or more. The amount of these curing agents [b] used is a curability comprising the epoxy resin [a] and the curing agent [b] and, if necessary, other reactive diluents [c] and / or additives [d]. The amount of the curing agent is not particularly limited as long as the composition is cured. For example, when an amine-based curing agent is used, the active hydrogen possessed by the curing agent is usually 0 with respect to the epoxy group contained in the curable composition. It is preferably in the range of 7 to 1.3 equivalents. When using an acid anhydride curing agent, it is usually preferable that the acid anhydride group of the curing agent is in the range of 0.5 to 1.3 equivalents relative to the epoxy group contained in the curable composition. . When using a phenol type hardening | curing agent, it is preferable normally that it is the range of 0.5-1.3 equivalent with respect to the epoxy group contained in a curable composition. When dicyandiamide is used, it is usually preferred that the active hydrogen possessed by dicyandiamide is in the range of 0.5 to 1.3 equivalents relative to the epoxy group contained in the curable composition. When imidazoles are used, it is usually preferably in the range of 0.1 to 10% by mass relative to the compound having an epoxy group in the curable composition.

  Moreover, it is preferable that the usage-amount of the hardening | curing agent hardened | cured by irradiation of an active energy ray is the range of 0.1-10 mass% normally with respect to the compound which has an epoxy group in a curable composition.

The other reactive diluent [c] is not particularly limited as long as it is a reactive diluent usually used in the epoxy resin composition other than diglycidyl ether (1). For example, n-butyl glycidyl ether, allyl glycidyl Monoglycidyl ethers such as ether, 2-ethylhexyl glycidyl ether, methylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, pt-butylphenyl glycidyl ether; 2-butyl-2-ethyl-1,3-propanediol , Neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, and other polyhydric alcohols obtained by reacting with epichlorohydrin Ethers; neodecanoic acid glycidyl ester, adipic acid diglycidyl ester, glycidyl esters such as dimer acid diglycidyl ester; glycidyl methacrylate, styrene oxide and the like. In particular, when a diglycidylated product of 1,9-nonanediol, that is, diglycidyl ether (2) is further used, the water absorption of a cured product obtained by curing the resulting curable composition tends to be low, which is preferable.
When adding other reactive diluent [c], the effect of the diglycidyl ether (1) of the present invention is not lost, usually 0.1 to 0.1% relative to all components in the curable composition. It is preferably in the range of 30% by mass, and more preferably in the range of 0.5 to 20% by mass.

Examples of the additive [d] added to the curable composition of the present invention as needed include modifiers such as polybutadiene and CTBN (terminal carboxylic acid-modified nitrile butadiene rubber); titanium oxide, carbon black, and lake red C. Pigments such as toluidine red and copper phthalocyanine; stabilizers such as 2,6-di-t-butyl-4-methylphenol and 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline; calcium carbonate , Barium sulfate, zinc oxide, kaolin clay, silica and other fillers; flame retardants such as aluminum hydroxide, magnesium hydroxide, decabromodiphenyl oxide and triphenyl phosphite; antifoaming agents such as acrylic copolymers and silicone Leveling agents such as fluorosurfactants; n-benzyldimethylamine, 2, , 6-Tris (dimethylaminomethyl) -phenol, imidazole, triphenylphosphine, tetra-n-butylphosphonium tetraphenylborate, trimethylammonium phenoxide, metal nitrate (magnesium nitrate, manganese nitrate, etc.), trifluoromethanesulfonic acid and its salts Curing accelerators such as magnesium perchlorate and calcium perchlorate; and sensitizers such as anthracene, perylene, thioxanthone and acetophenone.
When the additive [d] is added, the amount used is not particularly limited and may be arbitrarily determined according to the application.

  The curing condition of the curable composition of the present invention is not particularly limited because it varies depending on the epoxy resin [a], curing agent [b], other reactive diluent [c] and additive [d] used. When a curing agent that cures by heat is used, the curable composition is usually cured by heating in the range of 0 to 200 ° C. The heating time varies depending on the temperature, and is usually in the range of 30 minutes to 30 days if it is 0 to 40 ° C, and usually in the range of 10 minutes to 30 hours if it is 40 to 200 ° C. On the other hand, when a curing agent that is cured by irradiation with active energy rays is used, examples of the active energy rays include ultraviolet rays, electron beams, radiation, microwaves, and the like, which are cured by irradiating the curable composition with these. To do. The irradiation time of the active energy ray varies depending on the type and intensity, but is usually in the range of 0.1 second to 1 hour.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by this Example. The viscosity measurement, water absorption measurement, and tensile test in the following examples, comparative examples and reference examples were carried out as follows.

[1] Viscosity The viscosity of the diluted resin used in Examples 2 to 5 and Comparative Examples 1 and 2 below is 25 ° C. using a B-type viscometer (trade name: TVB-20L, manufactured by Tokimec Co., Ltd.). It was measured.
[2] Water Absorption Rate The water absorption rate was measured according to JIS K 7209 (Method A) except that the size of the test piece was 80 mm × 10 mm × 3 mm. That is, the test piece was immersed for 24 hours in distilled water maintained at 23 ° C. in a thermostatic bath, and the water absorption rate was calculated from the mass of the test piece before the test and the mass of the test piece after the test according to the following formula.
Water absorption (%) = (m ₂ −m ₁ ) / m ₁ × 100
Where m ₁ : mass of the test piece before the test (g)
m ₂ : Mass of the test piece after the test (g)
[3] Tensile test A tensile test was performed according to JIS K 7162. That is, according to JIS K 7161 9, a 1BA type small test piece defined in Annex A of JIS K 7162 is used with a universal material testing machine (manufactured by Instron, model number: 5566) with an air temperature of 25 ° C. and a humidity of 50%. Under the conditions, the test was conducted at a test speed of 2 mm / min, and the yield stress and the tensile modulus were measured.
[4] Izod impact test An Izod impact test was conducted in accordance with JIS K 7110. That is, a No. 1 B test piece with a width of 3 mm was tested using an Izod impact tester (manufactured by Toyo Seiki Seisakusho) under the conditions of an air temperature of 25 ° C. and a humidity of 50%. Was measured. The absorbed energy was calculated from the measured hammer swing-up angle after the test piece fracture according to 7 described in JIS K 7110 Annex 2.
Then, an Izod impact value was calculated from the calculated absorbed energy according to JIS K 7110-7-2.
The above measurement results are summarized in Table 1.

<Example 1> Synthesis of diglycidyl ether (1) In a 1 L three-necked flask equipped with a Dean-Stark receiver, 100.0 g (0.624 mol) of 2-methyl-1,8-octanediol, epichlorohydrin 346.3 g (3.743 mol) and 14.2 g (0.062 mol) of benzyltriethylammonium chloride were charged and purged with nitrogen. Next, the mixture was stirred while dropping 199.7 g (2.496 mol) of a 50% by mass aqueous sodium hydroxide solution over 1 hour, the temperature in the flask was 50 ° C., the pressure was 7.98 kPa, and epichlorohydrin and water were added. Water was removed by refluxing. After completion of the dropwise addition of the aqueous sodium hydroxide solution, the reaction was carried out for 2.5 hours at 50 ° C. and 7.98 kPa. The reaction mixture was cooled to room temperature and then filtered to remove unreacted sodium hydroxide and by-product sodium chloride. After adding 900 ml of diethyl ether to the obtained filtrate, it was washed 4 times with 50 ml of water. Epichlorohydrin and diethyl ether were distilled off from the obtained organic layer under reduced pressure (85 ° C./1.33 kPa). Then, 110.4 g (0.405 mol; yield 64.9%, purity 99.0%) of diglycidyl ether (1) was obtained by distillation under reduced pressure (150 ° C./0.047 kPa). The NMR measurement result of this diglycidyl ether (1) is shown below.

¹ H-NMR (500 MHz, CDCl ₃ , TMS) δ: 0.90 (d, 3H, J = 6.5 Hz), 1.05-1.15 (m, 1H) 1.20-1.44 (m 7H), 1.55-1.63 (m, 2H), 1.66-1.76 (m, 1H), 2.60-2.62 (m, 2H), 2.78-2.81. (M, 2H), 3.12-3.17 (m, 2H), 3.21-3.41 (m, 4H), 3.43-3.54 (m, 2H), 3.68-3 .72 (m, 2H)
¹³ C-NMR (125 MHz, CDCl ₃ , TMS) δ: 17.02, 26.06, 26.86, 29.69, 29.72, 33.42, 33.50, 44.29, 44.34, 50.90, 50.96, 71.48, 71.63, 71.69, 77.22

<Reference Example 1> Synthesis of diglycidyl ether (2) In a 1 L three-necked flask equipped with a Dean Stark receiver, 100.0 g (0.624 mol) of 1,9-nonanediol, 346.3 g of epichlorohydrin ( 3.743 mol) and 14.2 g (0.062 mol) of benzyltriethylammonium chloride were charged and purged with nitrogen. Then, 199.7 g (2.496 mol) of 50% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring, the temperature in the flask was 50 ° C., the pressure was 7.98 kPa, and epichlorohydrin and water were added. Water was removed by refluxing. After completion of the dropwise addition of the aqueous sodium hydroxide solution, the reaction was carried out for 2 hours at 50 ° C. and 7.89 kPa. The reaction mixture was cooled to room temperature and then filtered to remove unreacted sodium hydroxide and sodium chloride. After adding 900 ml of diethyl ether to the obtained filtrate, it was washed 4 times with 50 ml of water. Epichlorohydrin and diethyl ether were distilled off from the obtained organic layer under reduced pressure (85 ° C./1.33 kPa). Then, 111.7 g (0.410 mol; yield 65.7%, purity 98.5%) of diglycidyl ether (2) was obtained by distillation under reduced pressure (160 ° C./0.033 kPa).

<Example 2>
76.2 g of bisphenol A type epoxy resin (trade name: Epicoat 828; hereinafter simply referred to as “epoxy resin 1” manufactured by Japan Epoxy Resin Co., Ltd.) and 23.8 g of diglycidyl ether (1) obtained in Example 1 Were mixed to obtain “Diluted Resin A”. It was 600 mPa * s when the viscosity of the obtained dilution resin A was measured by the above-mentioned method. Thereafter, an amine curing agent (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epomate B002W, main component: 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa) was added to the diluted resin A Spiro [5.5] undecane; hereinafter referred to as “amine-based curing agent 1”) was mixed with 54.4 g to obtain a curable composition.
By measuring a 3 mm-thick cured product prepared from the curable composition obtained by the above-described method according to the method described in 3.3.3 of JIS K 7238-2, water absorption measurement and Izod impact Test specimens for testing were prepared. Specifically, two glass plates coated with an external release agent are faced to each other through a spacer having a thickness of 3 mm, and the curable composition is poured between them and left at room temperature for 24 hours, and subsequently at 80 ° C. By curing by heating for 3 hours, a cured product having a thickness of 3 mm was obtained. A test piece of 80 mm × 10 mm × 3 mm was cut out from the obtained cured product, and the water absorption was measured. On the other hand, the Izod impact test was carried out by applying a B notch (tip radius 1 mm, notch depth 2.54 mm) described in JIS K 7110 to the test piece. Also, a PET film is laid on a glass plate, a 170 mm × 170 mm × 2 mm cell is produced on the film, the curable composition is poured into the cell, the PET film is placed on the cell, and then the glass plate is placed. It was. The cured product having a thickness of 2 mm was obtained by allowing it to stand at room temperature for 24 hours, followed by heating at 80 ° C. for 3 hours to cure. A test piece for a tensile test was produced by punching the obtained cured product into the shape of a 1BA type small test piece defined in JIS K 7162 Annex A.
The measurement results using each test piece are shown in Table 1.

<Example 3>
76.6 g of epoxy resin 1, 17.6 g of diglycidyl ether (1) obtained in Example 1 and 5.8 g of diglycidyl ether (2) obtained in Reference Example 1 were mixed to obtain “Diluted Resin B”. Got. It was 600 mPa * s when the viscosity of the obtained dilution resin B was measured by the above-mentioned method. Thereafter, 54.3 g of the amine curing agent 1 was mixed with the diluted resin B to obtain a curable composition. A cured product for various measurements was obtained from the curable composition in the same manner as in Example 2, and physical properties were evaluated. The results are shown in Table 1.

<Example 4>
77.0 g of epoxy resin 1 and 11.5 g of diglycidyl ether (1) obtained in Example 1 and 11.5 g of diglycidyl ether (2) obtained in Reference Example 1 were mixed to obtain “Diluted Resin C”. Got. It was 600 mPa * s when the viscosity of obtained dilution resin CD was measured by the above-mentioned method. Thereafter, 54.3 g of the amine curing agent 1 was mixed with the diluted resin C to obtain a curable composition. A cured product for various measurements was obtained from the curable composition in the same manner as in Example 2, and physical properties were evaluated. The results are shown in Table 1.

<Example 5>
77.4 g of epoxy resin 1, 5.6 g of diglycidyl ether (1) obtained in Example 1 and 17.0 g of diglycidyl ether (2) obtained in Reference Example 1 were mixed to obtain “Diluted Resin D”. Got. It was 600 mPa * s when the viscosity of the obtained dilution resin D was measured by the above-mentioned method. Thereafter, 54.0 g of amine-based curing agent 1 was mixed with the diluted resin D to obtain a curable composition. A cured product for various measurements was obtained from the curable composition in the same manner as in Example 2, and physical properties were evaluated. The results are shown in Table 1.

<Comparative Example 1>
74.7 g of epoxy resin 1 and 25.3 g of 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Epolite 1600, equivalent to component [C]) were mixed to obtain “Diluted resin E " It was 600 mPa * s when the viscosity of the obtained dilution resin E was measured by the above-mentioned method. Thereafter, 52.8 g of the amine curing agent 1 was mixed with the diluted resin E to obtain a curable composition. A cured product for various measurements was obtained from the curable composition in the same manner as in Example 2, and physical properties were evaluated. The results are shown in Table 1.

<Comparative example 2>
78.8 g of epoxy resin 1 and monoglycidyl ether of monohydric alcohol having 12 to 13 carbon atoms (Dainippon Ink Co., Ltd., trade name: EPICLON 703, corresponding to component [C]) 21.2 g were mixed. “Diluted resin F” was obtained. It was 600 mPa * s when the viscosity of the obtained dilution resin F was measured by the above-mentioned method. Thereafter, 46.4 g of amine-based curing agent 1 was mixed with the diluted resin F to obtain a curable composition. A cured product for various measurements was obtained from the curable composition in the same manner as in Example 2, and physical properties were evaluated. The results are shown in Table 1.

From Table 1, when the diglycidyl ether (1) of the present invention was used as a reactive diluent to obtain a cured product (Examples 2 to 5), 1,6-hexanediol diglycidyl compound or 12 to 12 carbon atoms. The yield stress and the tensile elastic modulus are higher and the Izod impact value is inferiorly higher than when the cured product is obtained using only monoglycidyl ether of 13 monohydric alcohol as a reactive diluent (Comparative Examples 1 and 2). It is understood that the mechanical properties are excellent. In general, when diglycidyl ether is used as compared to the case where monoglycidyl ether is used, the water absorption of the resulting cured product is high (see Comparative Examples 1 and 2), but the diglycidyl ether of the present invention. When (1) is used (Examples 2 to 5), the water absorption is as low as when monoglycidyl ether is used (Comparative Example 2), and the water resistance is excellent.

Claims (4)

Following formula (1)

Diglycidyl ether represented by Following formula (1)

The curable composition containing the diglycidyl ether shown by these, epoxy resin [a], and hardening | curing agent [b]. Furthermore, the following formula (2)

The curable composition of Claim 2 containing the diglycidyl ether shown by these. Hardened | cured material formed by hardening | curing the curable composition of Claim 2 or 3.