JP2019104883A - Epoxy resin, epoxy resin composition, cured product, and method for producing epoxy resin - Google Patents

Abstract

To provide an epoxy resin and an epoxy resin composition capable of giving a cured product having a low halogen content and low colorability.SOLUTION: Provided is an epoxy resin represented by the following formula (1), in which a total chlorine content is 1-200 ppm as measured according to JIS K7243-3. (In formula (1), m and n are each independently an integer of 1 or more; Rand Reach independently represent a C1-12 divalent aliphatic group or a C6-40 divalent aromatic group; at least one of Rand Rrepresents a C6-40 divalent aromatic group; Grepresents a glycidyl group; and Grepresents a hydrogen atom or a glycidyl group).SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin, an epoxy resin composition, a cured product, and a method for producing an epoxy resin.

A cured product of an epoxy resin composition containing an epoxy resin and a curing agent is used in various applications including electronic members such as semiconductor packages and semiconductor chips, and optical members such as LEDs and camera modules.
For example, Patent Document 1 discloses a method for producing an epoxy resin having a polyether group having a repeating unit of 12 or less, which comprises a step of glycidylating an alcohol using an alkaline compound and a phase transfer catalyst.
In addition, Patent Document 2 discloses a method for producing an epoxy resin, which comprises a step of obtaining glycidyl ether by reacting an epihalohydrin with an alcohol using a solid acid catalyst to obtain an epihalohydrin ether and then reacting a base. There is. The epoxy resin in Patent Document 2 has a polyether group having a repeating unit of 4 or less, and in particular, in Example 4 of this document, the halogen atom content (chlorine content) is described as 0.08% (800 ppm). ing.

Patent No. 5860151 Patent No. 5101341

  In recent years, with regard to electronic members such as semiconductor packages and semiconductor chips, and optical members such as LEDs and camera modules, there has been an increasing demand for downsizing, thinning, and weight reduction. In particular, electronic devices that can be carried are required to have shock resistance that can operate properly even if they fall accidentally while satisfying the above requirements. Furthermore, from the viewpoint of corrosion resistance and electrical reliability, the electronic member is also desired to have a low content of halogen-based impurities, and to have low coloration from the viewpoint of light transparency to the optical member.

For example, the epoxy resin disclosed in Patent Document 1 contains a large amount of chlorine-containing by-products, and is considered to have a high degree of coloration because a high-concentration alkaline aqueous solution is used in the production of the epoxy resin.
Moreover, although the manufacturing method of glycidyl ether with few halogen atom containing impurities is disclosed by patent document 2, there exists room for further reducing and improving this halogen atom content.
Therefore, an epoxy resin having a small content of halogen-based impurities and a small color is required.

  The present invention is made in view of the above-mentioned circumstances, and it aims at providing an epoxy resin and an epoxy resin composition which can obtain a hardened material which has low halogen nature and low coloring nature.

  As a result of intensive investigations, the inventor of the present invention has found that the total chlorine content is within a specific range, and the epoxy resin represented by a specific structure has low halogenity and low colorability, and has completed the present invention. .

That is, the present invention is as follows.
[1]
The epoxy resin represented by following formula (1) whose total chlorine content measured by JISK7243-3 is 1-200 ppm or less.
(In formula (1), m and n are each independently an integer of 1 or more, and R ¹ and R ² are each independently a divalent aliphatic group having 1 to 12 carbon atoms, or Represents a divalent aromatic group having 6 to 40 carbon atoms, at least one of R ¹ and R ² represents a divalent aromatic group having 6 to 40 carbon atoms, and G ¹ represents a glycidyl group, G ² represents a hydrogen atom or a glycidyl group)
[2]
The epoxy resin as described in [1] whose Gardner color number measured by JISK0071-2 is 1.0-3.0.
[3]
The epoxy resin as described in [1] or [2] whose average addition number of the unit represented by -R < ¹ > O- is 5.0 or more per one molecule of an epoxy resin.
[4]
R ^{2 in the} formula (1) is any one selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (2) [ The epoxy resin as described in any one of 1]-[3].
(In formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms And X represents an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , and -S. Represents any one selected from the group consisting of -S-)
[5]
The epoxy resin in any one of [1]-[4] whose said Formula (1) is following formula (3).
(In formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, G ³ represents a hydrogen atom or a glycidyl group, and m and n each independently represent 1 The average addition number of the unit represented by -CH ₂ -CH (R ⁵ ) -O- is 5.0 or more and 12.0 or less per one molecule of epoxy resin.
[6]
(A) containing the epoxy resin according to any one of [1] to [5], (B) another epoxy resin, and (C) a curing agent,
The component (B) is 1 to 400 parts by mass based on 100 parts by mass of the component (A),
The resin composition whose said (C) component is 0.5-3.0 equivalent based on the epoxy group 1 equivalent of the said (A) component and the said (B) component.
[7]
The resin composition as described in [6] whose 50% destruction energy measured by JISK7211 is 4-20 J, when setting it as a hardened | cured material by making it harden | cure by making it harden | cure at 140 degreeC for 60 minutes, and also 220 degreeC for 120 minutes.
[8]
Hardened | cured material produced from the resin composition as described in [6] or [7].
[9]
An addition reaction step of adding an epihalohydrin to a polyol compound represented by the following formula (4) in the presence of a solid acid catalyst to obtain an epihalohydrin ether;
A ring closing reaction step of ring closing the epihalohydrin ether in the presence of an alkaline compound to obtain an epoxy resin;
The manufacturing method of the epoxy resin in any one of [1]-[5] including B.
(In the formula (4), m and n are each independently an integer of 1 or more, and R ¹ and R ² are each independently a divalent aliphatic group having 1 to 12 carbon atoms, or represents a divalent aromatic group having 6 to 40 carbon atoms, at least one of R ¹ and R ² is represented by.-R ¹ O-representing a divalent aromatic group having 6 to 40 carbon atoms The average addition number of units is 5.0 or more and 12.0 or less per molecule of the polyol compound.)

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin and the epoxy resin composition which can obtain the hardened | cured material which has low halogen property and low colorability can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the spirit of the present invention.

[Epoxy resin]
The epoxy resin of the present embodiment is represented by the following formula (1).

(In formula (1), m and n are each independently an integer of 1 or more, and R ¹ and R ² are each independently a divalent aliphatic group having 1 to 12 carbon atoms, or Represents a divalent aromatic group having 6 to 40 carbon atoms, at least one of R ¹ and R ² represents a divalent aromatic group having 6 to 40 carbon atoms, and G ¹ represents a glycidyl group, G ² represents a hydrogen atom or a glycidyl group)

The total chlorine content in the epoxy resin of the present embodiment is 1 to 200 ppm, preferably 1 to 150 ppm, more preferably 1 to 100 ppm. In addition, when the total chlorine content is in the range of 1 to 200 ppm, the impact resistance is further improved due to the small amount of impurities, and the coloring tends to be reduced.
The epoxy resin of this embodiment can be manufactured, for example, by the method of manufacturing an epoxy resin described later. Moreover, in the said manufacturing method, even if it does not implement a special process for removing a chlorine containing by-product, the total amount of chlorine can be controlled in the range of 1 to 200 ppm.

The Gardner hue in the epoxy resin of this embodiment is preferably 1.0 to 3.0, more preferably 1.5 to 3.0, and still more preferably 1.5 to 2.5. When the Gardner hue is 1.0 to 3.0, the number of double bond-containing by-products that cause coloring is small, and the impact resistance is further improved.
The Gardner color can be adjusted in the range of 1.0 to 3.0 by the method for producing an epoxy resin described later. Moreover, in the said manufacturing method, Gardner hue can be controlled in the range of 1.0-3.0, without implementing the special process for removing a double bond containing by-product.

In the formula (1), the divalent aliphatic group having 1 to 12 carbon atoms in R ¹ and R ² may be linear, branched or may contain an unsaturated bond group.
The carbon number of the divalent aliphatic group is preferably 1 to 6 from the viewpoint of the balance between flexibility and heat resistance, and more preferably 1 to 3 from the viewpoint of easiness of production.
As said bivalent aliphatic group, a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, isobutylene group, tert- butylene group, n-pentylene group, for example 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 1-ethylpropylene group, 1,1-dimethylpropylene group, 1,2-dimethylpropylene group, 2,2-dimethylpropylene group etc. are mentioned Be Among these, preferred are a methylene group, an ethylene group, an n-propylene group and an isopropylene group.

In the formula (1), examples of the divalent aromatic group having 6 to 40 carbon atoms as R ¹ and R ² include phenylene group, naphthylene group, biphenylene group; phenylene group, naphthylene group, biphenylene group; bisphenol A, Bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetramethylbiphenyl, tetrabromobiphenyl, diphenyl ether, benzophenone, phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutyl Examples thereof include divalent aromatics derived from any selected from the group consisting of hydroquinone, resorcine, methylresorcine, and catechol.

R ^{1 in the} formula (1) may be identical to or different from each other.

The epoxy resin of the present embodiment may contain one or more of at least one molecule included in the formula (1). At this time, the average addition number of units (also referred to as repeating units) represented by -R ¹ O- contained in the formula (1) is preferably 5.0 or more per one molecule of epoxy resin, More preferably, it is 5.5 or more, More preferably, it is 6.0 or more.
The upper limit of the average addition number is preferably 12.0 or less.
When the average addition number is 5.0 or more, the impact resistance is further improved, the viscosity can be further lowered, and the handling property tends to be further improved.
The “average number of additions” in the present embodiment is also defined as the average value of the sum of m and n in the formula (1) in the epoxy resin.

The epoxy equivalent of the epoxy resin of the present embodiment is preferably 200 to 500 g / eq. , More preferably 240 to 450 g / eq. , More preferably 300 to 370 g / eq. It is. Epoxy equivalent 200 to 500 g / eq. The impact resistance tends to be further improved by setting the range of
As a method of adjusting the range of epoxy equivalent, the method of controlling the quantity of the catalyst in manufacture of an epoxy resin, the method of controlling the quantity of the epihalohydrin which is a raw material, etc. are mentioned, for example.
The epoxy equivalent can be measured specifically by the method described in the examples.

In formula (1), when R ¹ is an aliphatic group, R ² is preferably an aromatic group, and when R ¹ is an aromatic group, R ² is an aliphatic group preferable.
R ² is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of viscosity, and is a divalent aromatic group having 6 to 15 carbon atoms from the viewpoint of easiness of production More preferable.

R ^{2 in the} formula (1) is any one selected from the group consisting of a phenylene group, a naphthylene group, and a divalent aromatic group having a structure represented by the following formula (2) from the viewpoint of heat resistance Is preferred.

(In formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms And X represents an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , and -S. Represents any one selected from the group consisting of -S-)

R ³ and R ⁴ are preferably each independently a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, an ethyl group or a tert-butyl group from the viewpoint of easy availability.

  Examples of the divalent aromatic group having a structure represented by the formula (2) include bisphenol A, bisphenol F, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, oxybiphenyl, dihydroxy benzophenone, 4-hydroxybenzoic acid 4-hydroxybenzene ester, bis (4-hydroxyphenyl) sulfide, 4,4'-sulfinyl Divalent aromatic groups derived from any one selected from the group consisting of bisphenol and bis (4-hydroxyphenyl) disulfide and the like can be mentioned.

  Formula (1) is preferably the following formula (3) from the viewpoint of impact resistance.

(In formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, G ³ represents a hydrogen atom or a glycidyl group. M and n each independently represent 1 The average addition number of the unit represented by -CH ₂ -CH (R ⁵ ) -O- is 5.0 or more and 12.0 or less per one molecule of epoxy resin.

G ³ in the formula (3) is preferably a glycidyl group from the viewpoint of water absorption and reaction rate.

It is preferable that m and n of Formula (3) are respectively independently an integer of 1-11.
Further, -CH ₂ -CH (R ⁵⁾ average addition number of -O- represented by units, is preferably 5.0 to 12.0. When the average addition number is 5.0 or more and 12.0 or less, the impact resistance is further improved, the viscosity can be further lowered, and the handling property is further improved.

[Method of producing epoxy resin]
The epoxy resin of the present embodiment can be produced, for example, by using a polyol compound represented by the following formula (4) as a raw material. The polyol compound represented by the polyol compound represented by Formula (4) is commercially available. The polyol compound represented by the formula (4) contains one or more of at least one compound included in the formula (4).

(In the formula (4), m and n are each independently an integer of 1 or more, and R ¹ and R ² are each independently a divalent aliphatic group having 1 to 12 carbon atoms, or represents a divalent aromatic group having 6 to 40 carbon atoms, at least one of R ¹ and R ² is represented by.-R ¹ O-representing a divalent aromatic group having 6 to 40 carbon atoms The average addition number of units is 5.0 or more and 12.0 or less per molecule of the polyol compound.)
The “average number of additions” in the formula (4) is also defined as the average value of the sum of m and n in the formula (4) in the polyol compound.

  As a method for producing the epoxy resin of the present embodiment, for example, an epoxy resin precursor (also referred to as an epihalohydrin ether) before ring closure by adding an epihalohydrin to the polyol compound represented by the formula (4) in the presence of a solid acid catalyst And a ring-closing reaction step of ring-closing the epihalohydrin ether in the presence of an alkaline compound to obtain an epoxy resin. The method will be described in detail below.

[Addition reaction process]
The addition reaction step of the above formula (4) and epihalohydrin can be carried out by either a batch method or a flow method. The batch method is a system in which the active hydroxyl compound and the epihalohydrin are reacted in a state where the catalyst is suspended in a stirred reaction vessel. The flow method is a method in which a fixed bed in which a container is filled with a catalyst is connected to a circulation tank, and a solution containing an active hydroxyl compound and an epihalohydrin is allowed to flow and react.

  The epihalohydrin is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin and the like. The amount of epihalohydrin added is usually 1.0 to 10.0 equivalents, preferably 1.2 to 6.0 equivalents, and more preferably based on one equivalent of the active hydroxyl group of the polyol compound in either the batch method or the flow method. Is 1.5 to 3.0 equivalents. When the addition amount of the epihalohydrin is 1.0 equivalent or more, the addition reaction proceeds sufficiently, and an epihalohydrin ether in which the epihalohydrin is added to at least one end of the polyol compound tends to be sufficiently obtained. By sufficiently obtaining the epihalohydrin ether, the epoxy resin obtained from such an epihalohydrin ether has an epoxy group sufficiently on at least one of the ends, and when it is a cured product, crosslinks are densely formed, and the impact resistance is excellent. Further, when the amount of the epihalohydrin added is 10 equivalents or less, side reactions can be suppressed, and a high purity epihalohydrin ether tends to be obtained.

  The solid acid catalyst is not particularly limited, and examples thereof include clay mineral, silica gel, cation exchange resin, porous metal oxide and the like. These may be used alone or in combination of two or more.

The clay mineral is a constituent unit of clay particles having a layered silicate mineral as a main component, and is classified into various types according to the substance contained in the interlayer.
Examples of commercial products of clay minerals include Montmorillonaite K-10 manufactured by Alfa Aesar, and Odosorb R-1 manufactured by Kurosaki Shirato Kogyo Co., Ltd.
Acidic white earth, which is one of clay minerals, is classified into activated white clay, synthetic zeolite and the like by treating acid white clay with a mineral acid such as sulfuric acid.
Examples of commercially available acid clay include Odo Earth 04 manufactured by Kurosaki Shirato Kogyo Co., Ltd., Nikkanite S-200 manufactured by Japan Activated White Clay Co., Ltd., Mizuka Ace # 20 manufactured by Mizusawa Chemical Industry Co., Ltd., and the like.
Examples of commercially available products of activated clay include activated clay R-15, Nippon Activated Shirato Co., Ltd. Nikkanite GCH-36, Galleon Earth NV, Mizusawa Chemical Industry Co., Ltd. Galeonite # 336 and the like.
Commercially available synthetic zeolites include synthetic zeolite F-9 manufactured by Wako Pure Chemical Industries, Ltd. Mizuka Chemical Co., Ltd. Mizuka sieves Y-420, manufactured by JGC Catalysts Chemical Corporation H-Y, ZSM-5, SAPO-5, etc. Can be mentioned.

  The silica gel solid acid catalyst is a spherical catalyst in which a sulfonic acid group or the like is modified on the surface of silica gel. As a commercial item of a silica gel type solid acid catalyst, Tayca Co., Ltd. Teika cure SAC-10 etc. are mentioned.

  The cation exchange resin is a spherical catalyst modified on the surface of polystyrene or acrylic resin with a sulfonic acid group and / or a carboxyl group. Commercially available products of the cation exchange resin include Duolite SC200 manufactured by Sumika Chemtex Co., Ltd., Amberlyst 15 DRY manufactured by Dow Chemical Co., and the like.

The porous metal oxide is a transition metal oxide such as titanium, zinc, yttrium, zirconium, niobium, tin, lanthanum, tantalum or the like; or a perovskite type oxide such as SrTiO ₃ or CaTiO ₃ by a template method or a firing method Are made porous.

  Among these solid acid catalysts, clay minerals, silica gel solid acid catalysts, and cation exchange resins are preferable from the viewpoint of easy availability, and clay minerals are more preferable from the viewpoint of high catalytic ability and low cost.

  The solid acid catalyst may be in the form of powder, granules, beads, pellets, chips, or in the form of a suspension dispersed in water or the like.

The addition amount of the solid acid catalyst is usually 10 to 90 g, preferably 20 to 80 g, more preferably 25 to 75 g based on one equivalent of the active hydroxyl group of the polyol compound in the case of a batch method. When the addition amount of the solid acid catalyst is 10 g or more, the reaction proceeds sufficiently, and an epihalohydrin ether in which the epihalohydrin is added to at least one of the ends of the polyol compound tends to be sufficiently obtained. In addition, when the addition amount of the solid acid catalyst is 90 g or less, side reactions such as self polymerization of epihalohydrin can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
The amount of the solid acid catalyst added is usually 200 to 1800 g, preferably 400 to 1600 g, more preferably 500 to 1500 g, in the case of the flow method, based on one equivalent of the active hydroxyl group of the polyol compound. When the addition amount of the solid acid catalyst is 200 g or more, the reaction proceeds sufficiently, and an epihalohydrin ether in which the epihalohydrin is added to at least one end of the polyol compound tends to be sufficiently obtained. Further, when the addition amount of the solid acid catalyst is not more than 1800 g, side reactions such as self polymerization of epihalohydrin can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
By sufficiently obtaining the epihalohydrin ether, the epoxy resin obtained from such an epihalohydrin ether has an epoxy group sufficiently on at least one of the ends, and when it is a cured product, crosslinks are densely formed, and the impact resistance is excellent.

  The reaction temperature is usually 25 to 140 ° C., preferably 30 to 130 ° C., and more preferably 40 to 120 ° C. in either of the batch method and the flow method. When the reaction temperature is 25 ° C. or more, the progress of the reaction becomes fast, so that the epihalohydrin tends to be able to be added efficiently. Further, when the reaction temperature is 140 ° C. or less, side reactions such as self polymerization of epihalohydrin can be efficiently suppressed, and a high purity epihalohydrin ether tends to be obtained.

The reaction time is usually 1 to 12 hours, preferably 2 to 10 hours, more preferably 4 to 8 hours in the case of a batch method. When the reaction time is 1 hour or more, the reaction proceeds sufficiently, and it tends to be possible to obtain an epihalohydrin ether in which an epihalohydrin is added to at least one of the ends of the polyol compound. In addition, when the reaction time is 12 hours or less, side reactions such as self polymerization of epihalohydrin can be suppressed, and a high purity epihalohydrin ether tends to be obtained.
In the case of the flow method, from the viewpoint of reaction rate, suppression of side reaction and suppression of catalyst deterioration due to pressure loss, the reaction time obtained by multiplying the number of times of liquid passage and contact time of catalyst and reaction liquid per one liquid passage It is 24 hours, preferably 2 to 18 hours, more preferably 4 to 12 hours. When the reaction time is 1 hour or more, the reaction proceeds sufficiently, and it tends to be possible to obtain an epihalohydrin ether in which an epihalohydrin is added to at least one of the ends of the polyol compound. In addition, when the reaction time is 24 hours or less, side reactions such as self polymerization of epihalohydrin and reaction gradients due to pressure loss can be suppressed, and a high purity epihalohydrin ether tends to be obtained.

  In either of the batch method and the flow method, the reaction may be performed without a solvent, or may be performed using a solvent. The solvent is not particularly limited, but nonpolar solvents such as hexane, toluene, xylene, ethyl acetate, chloroform etc .; acetone, acetonitrile, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, dimethyl sulfoxide etc. Polar aprotic solvents; polar protic solvents such as methanol, ethanol and 1-propanol; water and the like. These solvents may be used alone or in combination of two or more.

  Among the above solvents, nonpolar solvents and polar protic solvents are preferable from the viewpoint of reaction inhibition, and nonpolar solvents are more preferable from the viewpoint of reaction control.

  After completion of the addition reaction, the reaction solution and the solid acid catalyst are preferably separated by filtration, centrifugation, decantation or the like. Next, the separated reaction liquid is heated under normal pressure or reduced pressure to remove the remaining epihalohydrin and recover epihalohydrin ether.

  The separated solid acid catalyst can be used again for the reaction by regeneration by washing, air drying, heating or the like.

[Closing reaction step]
The ring closure reaction step is a step for obtaining an epoxy resin by ring closure of the epihalohydrin ether obtained by the addition reaction step in the presence of an alkaline compound.

The alkaline compound is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, barium hydroxide, potassium carbonate and the like. These may be used alone or in combination of two or more.
The state of the alkaline compound is not particularly limited, and may be, for example, a solid, liquid, aqueous solution, alcohol solution or the like.
The addition amount of the alkaline compound is usually 1 to 10 equivalents, preferably 1.2 to 5.0 equivalents, more preferably 1.5 to 3.0 equivalents, based on 1 equivalent of the active hydroxyl group of the epihalohydrin ether. When the addition amount of the alkaline compound is 1 equivalent or more, the reaction proceeds sufficiently, and it tends to be possible to obtain an epoxy resin in which the epihalohydrin is sufficiently closed. When the addition amount of the alkaline compound is 10 equivalents or less, the polymerization reaction of the epihalohydrin and the epoxy resin can be suppressed, and an epoxy resin with high purity tends to be obtained.

  In the cyclization reaction step, a phase transfer catalyst is preferably used from the viewpoint of promoting the reaction. In particular, it is more preferable to use the above-mentioned alkaline compound and the phase transfer catalyst in combination.

The phase transfer catalyst is not particularly limited. For example, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, benzyl Quaternary ammonium salts such as trimethyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, phenyltrimethyl ammonium chloride and the like; tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide and the like; Grade ammonium hydroxides; Crown ethers such as 5-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, diaza-18-crown-6, etc. [2.1.1] -cryptand And cryptands such as [2.2.1] -cryptand, [2.2.2] cryptand, [2.2.2] -decyl cryptand, [2.2.2] -benzocryptand and the like. Be These may be used alone or in combination of two or more.
The state of the phase transfer catalyst is not particularly limited, and may be, for example, a solid, liquid, aqueous solution, alcohol solution or the like.

  The amount of phase transfer catalyst added is usually 0.005 to 1 mol, preferably 0.01 to 0.1 mol, based on 1 mol of the active hydroxyl group of the epihalohydrin ether. When the addition amount of the phase transfer catalyst is 0.005 mol or more, the reaction proceeds sufficiently, and the epihalohydrin tends to be able to obtain an epoxy resin sufficiently closed. In addition, when the addition amount of the phase transfer catalyst is 1 mole or less, the phase transfer catalyst tends to be sufficiently removed from the epoxy resin composition by water washing or the like.

  The reaction temperature is generally 25 to 100 ° C., preferably 30 to 80 ° C. When the reaction temperature is 25 ° C. or more, the progress of the reaction becomes fast, and thus the epihalohydrin ether tends to be able to be ring-closed efficiently. In addition, when the reaction temperature is 100 ° C. or less, the polymerization reaction of the epihalohydrin ethers can be suppressed, and the epihalohydrin ether tends to be able to be ring-closed efficiently.

  The reaction time is usually 0.5 to 12 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours. When the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and the epihalohydrin ether tends to be able to be closed efficiently. In addition, when the reaction time is 12 hours or less, the polymerization reaction of the epihalohydrin ethers can be suppressed, and the epihalohydrin ether tends to be able to be ring-closed efficiently.

  In the cyclization reaction step, the reaction may be carried out without a solvent, or the reaction may be carried out using a solvent. The solvent is not particularly limited, but nonpolar solvents such as hexane, toluene, xylene, ethyl acetate, chloroform etc .; acetone, acetonitrile, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, dimethyl sulfoxide etc. Polar aprotic solvents; polar protic solvents such as methanol, ethanol and 1-propanol; water and the like. These solvents may be used alone or in combination of two or more.

  Among the above solvents, nonpolar solvents and polar protic solvents are preferred from the viewpoint of preventing the progress of the reaction from being inhibited, and toluene, methyl ethyl ketone and methyl isobutyl ketone are more preferred from the viewpoint of reaction control and recovery ease.

  It is preferable to remove the formed salt, the remaining alkaline compound, the phase transfer catalyst and the like from the reaction solution by, for example, water washing after completion of the ring closure reaction. Then, the solvent can be removed from the reaction solution, for example, by heating the reaction solution under normal pressure or reduced pressure, and the epoxy resin can be recovered.

[Epoxy resin composition]
The epoxy resin composition of the present embodiment is not particularly limited as long as it contains (A) the epoxy resin of the present embodiment (also referred to as a single “(A) component” in the present specification). The epoxy resin of the embodiment, (B) another epoxy resin (also referred to simply as “component (B)” herein), and (C) a curing agent (only “component (C)” herein) And the component (B) is 1 to 400 parts by mass based on 100 parts by mass of the component (A), and the total epoxy group 1 of the component (A) and the component (B) It is preferable that the said (C) component is 0.5-3.0 equivalent based on an equivalent. Each component is described in detail below.

[(B) Other epoxy resin]
(B) Other epoxy resins are epoxy resins other than the above-mentioned (A) ingredient. As the component (B), for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, tetrabromobisphenol A epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, tetrabromobiphenyl Type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene Type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin And bifunctional epoxy resins such as resorcinol type epoxy resin, methyl resorcinol type epoxy resin, catechol type epoxy resin, N, N-diglycidyl aniline type epoxy resin; N, N-diglycidyl aminobenzene type epoxy resin, o- Trifunctional epoxy resins such as (N, N-diglycidylamino) toluene type epoxy resin, triazine type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, diaminobenzene type epoxy resin; phenol Novolak type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, brominated phenol no Polyfunctional epoxy resins of the rack-type epoxy resin or the like; and alicyclic epoxy resins and the like. Furthermore, epoxy resin etc. which modified these with isocyanate etc. can be used together.

  Based on 100 parts by mass of the component (A) in the epoxy resin composition of the present embodiment, the amount of the component (B) is 1 to 400 parts by mass, preferably 20 to 300 parts. When the component (B) is 1 part by mass or more, microphase separation occurs, and a cured product having good strength tends to be obtained while having sufficient impact resistance. In addition, when the component (B) is 400 parts by mass or less, a cured product having good impact resistance tends to be obtained while having sufficient strength.

[(C) curing agent]
The curing agent (C) is not particularly limited, and examples thereof include acid anhydride curing agents, amine curing agents, phenol curing agents, latent curing agents, and catalyst curing agents.

  As the acid anhydride curing agent, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, Methyl hexahydrophthalic anhydride etc. are mentioned.

Examples of the amine curing agent include aliphatic amines and aromatic amines.
Examples of aliphatic amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane And bis (4-aminocyclohexyl) methane, norbornene diamine, 1,2-diaminocyclohexane and the like.
Examples of the aromatic amine include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylene bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate and the like.

  As a phenol type curing agent, for example, phenol novolak resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified phenol resin, aminotriazine modified resin Phenol resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, allyl acrylic phenol resin and the like can be mentioned.

  Examples of latent curing agents include imidazole compounds, dicyandiamide and derivatives thereof, amine-epoxy adducts, amine-urea adducts, curing agents formed by coating these, curing agents formed by complexing with inclusion compounds, The curing agent etc. which make it adsorb | suck to a porous body are mentioned. As the latent curing agent, specifically, Novacuer HX-3721, HX-3722, HX-3613, HX-3921HP, HXA4922HP, HXA5945HP manufactured by Asahi Kasei Co., Ltd .; 40J, MY-24; Fujicure FXR-1020 manufactured by Fuji Kasei Kogyo Co., Ltd., FXR-1030, and the like.

As a catalyst type curing agent, a cationic thermosetting catalyst, BF ₃ -amine complex, etc. are mentioned, for example.

These curing agents may be used alone or in combination of two or more.
Among the above-mentioned curing agents, amine-based curing agents are preferable from the viewpoint of flexibility and adhesiveness. In addition, from the viewpoint of heat resistance and low water absorption, a phenolic curing agent is preferable.

  Component (C) is 0.5 to 3.0 equivalents, preferably 0, based on one equivalent of the total epoxy group of the components (A) and (B) in the epoxy resin composition of the present embodiment. .8 to 2.0 equivalents. When the amount of the component (C) is 0.5 equivalent or more, a cured product having a sufficient degree of crosslinking density to develop impact resistance tends to be obtained. When the amount of the component (C) is 3.0 equivalents or less, a cured product having sufficient impact resistance tends to be obtained regardless of the physical properties of the cured product.

  The epoxy resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazole-based curing accelerators such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol, 1, Tertiary amine curing accelerators such as 5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] undec-7-ene; phosphorus systems such as triphenylphosphine Curing accelerators; organic acid metal salts; Lewis acids; amine complex salts and the like. The curing reaction can be accelerated by using these in combination with the above-mentioned curing agent. An appropriate type of curing accelerator can be selected according to the type of curing agent described above.

  In the epoxy resin composition of the present embodiment, the content of the curing accelerator is not particularly limited as long as the effects of the present embodiment can be obtained. The content of the curing accelerator is usually preferably 0.1 to 5.0 parts by mass based on 100 parts by mass of the total amount of epoxy resin. When the content of the curing accelerator is 0.1 to 5.0 parts by mass, the curing reaction is sufficiently accelerated, and it is likely that better cured physical properties can be obtained.

  The epoxy resin composition of the present embodiment may further contain an inorganic filler, if necessary. The inorganic filler is not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride and the like.

  The content of the inorganic filler in the epoxy resin composition of the present embodiment is not particularly limited as long as the effects of the present embodiment can be obtained. Usually, it is preferable that it is 90 mass% or less of the epoxy resin composition of this embodiment. By setting the content of the inorganic filler to 90% by mass or less, the viscosity of the epoxy resin composition is sufficiently low, and the handling property tends to be excellent.

  The epoxy resin composition of the present embodiment may further contain other compounding agents such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as necessary. As long as the effects of the present embodiment can be obtained, suitable ones can be appropriately selected. For example, the flame retardant is not particularly limited, and examples thereof include halides, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds and the like.

  The 50% breaking energy of the cured product obtained by curing at 140 ° C. for 60 minutes and further at 220 ° C. for 120 minutes in the epoxy resin composition of the present embodiment is preferably 4 to 20 J, more preferably 5 to 15 J More preferably, it is 5 to 10 J. When the 50% breaking energy is 4 J or more, sufficient impact resistance can be obtained, and peeling and cracking from the adhesive surface tend to be less likely to occur due to impact or the like. When the 50% destruction energy is 20 J or less, the impact energy generated due to the drop or the like is less likely to propagate to the adherend or other adhesion site, so the destruction of the adherend or the peeling off of other adhesion sites can be suppressed. There is a tendency.

The cured product of the present embodiment is a cured product produced from the resin composition of the present embodiment and cured by curing the epoxy resin composition of the present embodiment.
The cured product of the present embodiment can be obtained by, for example, thermally curing the above-mentioned epoxy resin composition by a conventionally known method or the like. Specifically, the cured product of the present embodiment can be obtained by the following method.
First, until the epoxy resin of the present embodiment, a curing agent, and, if necessary, a curing accelerator, an inorganic filler, and / or a compounding agent, etc. are uniformed using an extruder, a kneader, a roll, etc. The mixture is thoroughly mixed to obtain an epoxy resin composition. Thereafter, the epoxy resin composition is molded using a casting or transfer molding machine, a compression molding machine, an injection molding machine or the like, and is further heated at about 60 to 250 ° C. under conditions of about 1 minute to 10 hours. You can get things.

Moreover, the hardened | cured material of this embodiment can also be obtained by the following method.
First, the epoxy resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone and methyl isobutyl ketone to obtain a solution. The obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like, and dried by heating to obtain a prepreg. Next, a cured product can be obtained by subjecting the obtained prepreg to hot press molding.

  The epoxy resin composition of the present embodiment is excellent in impact resistance and further has transparency. Therefore, the epoxy resin composition of the present embodiment can be suitably used as a sealing material or an adhesive in electronic members such as semiconductor packages and semiconductor chips, and optical members such as LEDs and camera modules.

  The epoxy resin composition of the present embodiment and the molded product made of the cured product thereof can be used in various applications where an epoxy resin is used as a material. Although it does not specifically limit as a use, Optical member sealing materials, such as LED and a camera module, are preferable. In addition, as applications, semiconductor encapsulation materials such as underfill and molding, conductive adhesives such as anisotropic conductive film (also referred to as ACF), printed wiring boards such as solder resist and cover lay film, etc. Used.

  Next, the present invention will be more specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. In the following, "parts" and "%" are based on mass unless otherwise noted.

  The measuring method of each physical property was as follows.

(1) Epoxy equivalent The epoxy equivalent was measured based on JISK7236 for the epoxy resin mentioned later.

(2) Total chlorine content The total chlorine content was measured based on JISK7243-3 for the epoxy resin mentioned later.

(3) Gardner color number Gardner color number was measured based on JISK0071-2 for the epoxy resin mentioned later.

(4) 50% destruction energy 50% destruction energy was measured based on JISK7211 for the hardened | cured material mentioned later.

Example 1
(Addition reaction process)
In a glass jacketed reactor equipped with a thermometer, a dropping funnel, a condenser and a stirrer, ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl group Value: 228 mg KOH / g 100 g, solid acid catalyst; 10 g of Nikkanite GCH-36 (trade name) manufactured by Nippon Activated Shirato Co., and 80 g of toluene were mixed. The mixture was stirred and suspended at 80 ° C. while introducing nitrogen into the reactor. Then, 56 g of epichlorohydrin was dropped over 2 hours. After dropping, the mixture was allowed to react for 4 hours, then the mixture was cooled, and the reaction solution and the solid acid catalyst were separated by decantation. The reaction solution was pressure-filtered with a membrane filter, and excess epichlorohydrin was removed by distillation under reduced pressure from the obtained filtrate to obtain epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain epoxy resin A-1.

Example 2
An epoxy resin A-2 was obtained in the same manner as in Example 1 except that the amount of the solid acid catalyst was changed to 31 g.

[Example 3]
An epoxy resin A-3 was obtained in the same manner as in Example 1 except that the amount of the solid acid catalyst was changed to 20 g and the amount of epichlorohydrin was changed to 113 g.

Example 4
An epoxy resin A-4 was obtained in the same manner as in Example 3 except that the amount of epichlorohydrin was changed to 75 g.

[Example 5]
An epoxy resin A-5 was obtained in the same manner as in Example 4 except that the type of solid acid catalyst was changed to Nippon Activated Shirato Co., Ltd .; trade name "Nikkanite S-200".

[Example 6]
An epoxy resin A-6 was obtained in the same manner as in Example 4 except that the type of solid acid catalyst was changed to JGC Catalyst Chemical Co., Ltd .; trade name "ZSM-5".

[Example 7]
Example except changing the kind of solid acid catalyst into the brand name "Taikacure SAC-10" made by Tayca Co., Ltd., changing the amount of solid acid catalyst to 24 g and changing the amount of epichlorohydrin to 71 g It carried out like 1 and obtained epoxy resin A-7.

[Example 8]
(Addition reaction process)
In a glass jacketed reactor equipped with a thermometer and a stirrer, ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl value: 228 mg KOH / g 100 g, 113 g of epichlorohydrin and 80 g of toluene were mixed. The mixture was stirred and suspended at 80 ° C. while introducing nitrogen into the reactor. Solid acid catalyst; Nippon Activated Shirato Co., Ltd. product name "Nikkanite GCH-36" Trade name: "Nickanite GCH-36" After connecting the inlet side and outlet side of the fixed bed made of stainless steel to the reactor, the reaction liquid is circulated by pump for 8 hours I did. The fixed bed residence time of the reaction solution per cycle was about 2 minutes, and the number of cycles was about 200 times. After completion of the reaction, excess epichlorohydrin was removed by distillation under reduced pressure from the reaction solution to obtain epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain epoxy resin A-8.

[Example 9]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to 10 mol adduct of bisphenol A ethylene oxide; manufactured by Sanyo Chemical Industries Ltd. trade name “ Hydroxyl value: changed to 167 mg KOH / g, the amount of solid acid catalyst was changed to 15 g, the amount of epichlorohydrin was changed to 56 g, the solvent was changed to methyl ethyl ketone, the reaction time was changed An epoxy resin A-9 was obtained in the same manner as in Example 1 except that the time was changed to 8 hours.

[Example 10]
The type of solid acid catalyst was changed to Taika Co., Ltd. under the trade name "Taikacure SAC-10", the amount of solid acid catalyst was changed to 22 g, the amount of epichlorohydrin was changed to 83 g, and the reaction time was 7 hours The epoxy resin A-10 was obtained in the same manner as in Example 9 except for changing to.

[Example 11]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to propylene oxide 5 mol adduct of bisphenol A; trade name made by Sanyo Chemical Industries, Ltd. "Neupol BP-5P"; hydroxyl value: changed to 211 mg KOH / g, changed amount of solid acid catalyst to 19 g, changed amount of epichlorohydrin to 53 g as in Example 1 To obtain an epoxy resin A-11.

[Example 12]
An epoxy resin A-12 was obtained in the same manner as in Example 11 except that the amount of epichlorohydrin was changed to 71 g.

[Example 13]
An epoxy resin A-13 was obtained in the same manner as in Example 12 except that the amount of the solid acid catalyst was changed to 29 g.

Example 14
An epoxy resin A-14 was obtained in the same manner as in Example 12 except that the type of solid acid catalyst was changed to a product name "ZSM-5" manufactured by JGC Co., Ltd.

[Example 15]
An epoxy resin A-15 was obtained in the same manner as in Example 12 except that the type of solid acid catalyst was changed to Dow Chemical Co., Ltd. trade name "Amberlyst 15 DRY".

[Example 16]
An epoxy resin A-16 was obtained in the same manner as in Example 12 except that the type of the solid acid catalyst was changed to Taika Co., Ltd. trade name "Taikacure SAC-10".

[Example 17]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to propylene oxide 5 mol adduct of bisphenol A; trade name made by Sanyo Chemical Industries, Ltd. "Neupol BP-5P"; hydroxyl value: changed to 211 mg KOH / g, changed amount of solid acid catalyst to 462 g, changed amount of epichlorohydrin to 107 g, as in Example 1 The epoxy resin A-17 was obtained.

[Example 18]
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to ethylene oxide 4 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries Ltd. trade name “ Newpole BPE-40 "; hydroxyl value: changed to 276 mg KOH / g, changed amount of solid acid catalyst to 19 g, changed amount of epichlorohydrin to 72 g, and changed reaction time to 5 hours Were carried out in the same manner as in Example 1 to obtain an epoxy resin A-18.

[Example 19]
An epoxy resin A-19 was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin was changed to 45 g.

[Example 20]
An epoxy resin A-20 was obtained in the same manner as in Example 4 except that the amount of the solid acid catalyst was changed to 8 g.

[Example 21]
An epoxy resin A-21 was obtained in the same manner as in Example 4 except that the amount of the solid acid catalyst was changed to 33 g.

Example 22
Ethylene oxide 4 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-40”; hydroxyl value: 276 mg KOH / g to propylene oxide 3 mol adduct of bisphenol A; trade name manufactured by Sanyo Chemical Industries, Ltd. "Neupol BP-3P"; hydroxyl value: changed to 280 mg KOH / g, the amount of solid acid catalyst was changed to 25 g, and the amount of epichlorohydrin was changed to 92 g as in Example 18 The epoxy resin A-22 was obtained.

Comparative Example 1
An epoxy resin A-23 was obtained in the same manner as in Example 3 except that the amount of epichlorohydrin was changed to 225 g.

Comparative Example 2
(Addition reaction process)
In a glass jacketed reactor equipped with a thermometer, a dropping funnel, a condenser and a stirrer, ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl group 100 mg of epichlorohydrin and 4 g of 50% by mass aqueous tetramethylammonium chloride solution were mixed, heated under reduced pressure, and refluxed at 60.degree. And 162 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours. During the addition, water was continuously removed as an azeotropic mixture with epichlorohydrin, and only the condensed epichlorohydrin layer was continuously returned to the reactor. After dropping, the mixture was allowed to react for another 2 hours, and then the mixture was cooled and washed with water repeatedly to remove by-produced sodium chloride. The excess epichlorohydrin was distilled off under reduced pressure to give epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain epoxy resin A-24.

Comparative Example 3
Ethylene oxide 10 molar adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-100”, hydroxyl value: 167 mg KOH / g to ethylene oxide 18 molar adduct of bisphenol A; manufactured by Sanyo Chemical Industries Ltd. trade name “ Newpole BPE-180 "; hydroxyl value: changed to 110 mg KOH / g, changed amount of solid acid catalyst to 10 g, changed amount of epichlorohydrin to 36 g, and changed reaction time to 10 hours Were carried out in the same manner as in Example 9 to obtain an epoxy resin A-25.

Comparative Example 4
Ethylene oxide 6 mol adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd. trade name “New pole BPE-60”; hydroxyl value: 228 mg KOH / g to propylene oxide 5 mol adduct of bisphenol A; trade name made by Sanyo Chemical Industries, Ltd. “New pole BP-5P”; hydroxyl value: changed to 211 mg KOH / g, changed amount of epichlorohydrin to 172 g, changed amount of 50% by mass aqueous sodium hydroxide solution to 148 g, Comparative Example It carried out similarly to 2, and obtained epoxy resin A-26.

Comparative Example 5
(Addition reaction process)
In a glass jacket-type reactor equipped with a thermometer and a stirrer, 5 mol of propylene oxide adduct of bisphenol A; manufactured by Sanyo Chemical Industries, Ltd .; trade name "New Pole BP-5P"; hydroxyl value: 211 mg KOH / g 100 g A mixture of 172 g of epichlorohydrin, 52 g of flaky sodium hydroxide and 4 g of 50% by mass aqueous solution of tetramethylammonium chloride was heated under normal pressure and reacted at 60 ° C. for 8 hours. After completion of the reaction, the mixture was cooled and repeatedly washed with water to remove by-produced sodium chloride. The excess epichlorohydrin was distilled off under reduced pressure to give epihalohydrin ether.
(Closing reaction process)
100 g of the obtained epihalohydrin ether is dissolved in 100 g of toluene, and 1.5 equivalents of 50% by mass aqueous sodium hydroxide solution is added based on 1 equivalent of active hydroxyl group of epihalohydrin ether, and further based on 1 equivalent of active hydroxyl group of epihalohydrin ether Then, 0.01 equivalent of 50% by mass of tetramethylammonium chloride aqueous solution was added and reacted at 80 ° C. for 2 hours. After completion of the reaction, the reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed by distillation under reduced pressure from the reaction product to obtain an epoxy resin A-27.

Comparative Example 6
Ethylene oxide 6 mole adduct of bisphenol A; Sanyo Chemical Industries, Ltd. trade name "New pole BPE-60"; hydroxyl value: changed from 228 mg KOH / g to bisphenol A; hydroxyl value: 489 mg KOH / g, amount of solid acid catalyst Was changed to 44 g, the amount of epichlorohydrin was changed to 162 g, and the reaction time was changed to 4 hours, in the same manner as in Example 1, to obtain an epoxy resin A-28.

Comparative Example 7
Bisphenol A; hydroxyl value: 489 mg KOH / g to bisphenol F; hydroxyl value: 558 mg KOH / g, the amount of solid acid catalyst was changed to 50 g, and the amount of epichlorohydrin was changed to 185 g It carried out similarly to Example 6, and obtained epoxy resin A-29.

  The epoxy equivalent weight, total chlorine content and Gardner color number of the epoxy resins A-1 to A-22 obtained in Examples 1 to 22 and the epoxy resins A-23 to A-29 obtained in Comparative Examples 1 to 7 It was measured. The results are shown in Tables 1 to 3.

[Examples 23 to 53, Reference Examples 1 to 7]
As shown in Tables 4 to 7, (A) epoxy resin obtained in Examples 1 to 22 and Comparative Examples 1 to 7; A-1 to A 29 and (B) other epoxy resins; Name "CEL 2021 P", product name "EXA850 CRP" manufactured by DIC Corporation or product name "EXA 830 CRP" manufactured by DIC Corporation (C) acid anhydride based on 1 equivalent of epoxy group; product name "HN" manufactured by Hitachi Chemical Co., Ltd. -5500 "molecular weight 168 is added in a proportion of 0.96 equivalents, and (D) a curing accelerator based on a total of 100 parts by weight of the (A) component and the (B) component; 2-ethyl-4-methylimidazole One part by weight of (also referred to as 2E4MZ) was added to obtain an epoxy resin composition.
The obtained epoxy resin composition was poured into a 100 mm × 100 mm × 2 mm fluorine resin plate mold and cured in an oven at 140 ° C., 60 minutes and 220 ° C., 120 minutes to obtain a cured epoxy resin product. . The 50% breaking energy of the obtained cured product was measured using a Dupont impact tester H50.

  The evaluation results of Examples 23 to 53 and Reference Examples 1 to 7 are shown in Tables 4 to 7. In Tables 6 and 7, "-" at 50% breaking energy in Example 47 and Reference Example 3 could not be quantified because the measurement sample was flexible but lacked strength and was broken without breaking. Indicates that.

The resins of Examples 1 to 22, that is, epoxy resins: A-1 to A-22, all had a total chlorine content of 200 ppm or less and a Gardner color number of 3 or less.
Among the resins of Comparative Examples 1 to 7, that is, the epoxy resins: A-23 to A-29, the resins of Comparative Examples 1 to 5, that is, the epoxy resins: A-23 to 27 all have a total chlorine content of 200 ppm. As mentioned above, the Gardner color number was 3.5 or more.
Resins of Comparative Examples 1 to 7, that is, among epoxy resins: A-23 to A-29, resins of Comparative Examples 6 to 7, that is, all of epoxy resins: A-28 to A-29, the total chlorine amount Was 200 ppm or more, and the Gardner color number was 3 or less.

Epoxy resins: Examples 23 to 46 using A-1 to A-17 all had a 50% breaking energy value of 4 J or more.
Example 47 in which the component (B) was at most 20 parts by weight based on 100 parts by mass of the component (A) in the epoxy resin composition was a soft but brittle but brittle cured product.
Example 48 in which the component (B) was at least 300 parts by weight based on 100 parts by weight of the component (A) in the epoxy resin composition had a 50% breaking energy of less than 4 J.
In Examples 49 and 53 and Reference Examples 6 to 7 in which (m + n) in the above formula (1) is less than 5, the 50% destruction energy was less than 4 J in all cases.
The amount of epichlorohydrin added is 1.5 equivalents or less based on one equivalent of the active hydroxyl group of the polyol compound, Example 50 the amount of epichlorohydrin added based on one equivalent of the active hydroxyl group of the polyol compound The 50% destruction energy was less than 4 J in all of Reference Example 1 of 3 equivalents or more.
Example 51 in which the amount of solid acid catalyst added is less than 25 g based on one equivalent of the active hydroxyl group of the polyol compound, the amount of solid acid catalyst added exceeds 75 g based on one equivalent of the active hydroxyl group of the polyol compound In each of Example 52, 50% destruction energy was less than 4 J.
The 50% destruction energy was less than 4 J in all of Reference Examples 2 and 4-5 in which the total chlorine content of the component (A) is 200 ppm or more and the Gardner color number is 3.5 or more.
The reference example 3 in which (m + n) in the above formula (1) exceeds 10 is a soft but weak strength and a brittle cured product.

  From the above results, among the examples satisfying the low halogen property and the low coloring property, Examples 23 to 46 further satisfy the impact resistance. Although the reference examples 6 and 7 satisfy the low colorability, they do not satisfy the low halogen and impact resistance. The reference examples 1 to 5 do not satisfy any of the low halogen property, the low coloring property, and the impact resistance.

  According to the present invention, it is possible to provide an epoxy resin and an epoxy resin composition having low chlorination and low colorability and capable of obtaining a cured product, and further a cured product having excellent impact resistance. Particularly, it is useful as an encapsulating material and adhesive agent in electronic components such as semiconductor packages and semiconductor chips which require impact resistance, and optical components such as LEDs and camera modules, so that the utility in industry is high. .

Claims (9)

The epoxy resin represented by following formula (1) whose total chlorine content measured by JISK7243-3 is 1-200 ppm or less.
(In formula (1), m and n are each independently an integer of 1 or more, and R ¹ and R ² are each independently a divalent aliphatic group having 1 to 12 carbon atoms, or Represents a divalent aromatic group having 6 to 40 carbon atoms, at least one of R ¹ and R ² represents a divalent aromatic group having 6 to 40 carbon atoms, and G ¹ represents a glycidyl group, G ² represents a hydrogen atom or a glycidyl group)   The epoxy resin according to claim 1, wherein the Gardner color number measured by JIS K0071-2 is 1.0 to 3.0. The epoxy resin of Claim 1 or 2 whose average addition number of the unit represented by -R < ¹ > O- is 5.0 or more per one molecule of an epoxy resin. The R ^{2 in the} above formula (1) is any one selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (2) The epoxy resin as described in any one of claim 1 to 3.
(In formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms And X represents an alkylene group having 1 to 10 carbon atoms, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , and -S. Represents any one selected from the group consisting of -S-) The epoxy resin as described in any one of Claims 1-4 whose said Formula (1) is following formula (3).
(In formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, G ³ represents a hydrogen atom or a glycidyl group, and m and n each independently represent 1 The average addition number of the unit represented by -CH ₂ -CH (R ⁵ ) -O- is 5.0 or more and 12.0 or less per one molecule of epoxy resin. (A) containing the epoxy resin according to any one of claims 1 to 5, (B) another epoxy resin, and (C) a curing agent,
The component (B) is 1 to 400 parts by mass based on 100 parts by mass of the component (A),
The resin composition whose said (C) component is 0.5-3.0 equivalent based on the epoxy group 1 equivalent of the said (A) component and the said (B) component.   The resin composition according to claim 6, wherein the 50% breaking energy measured according to JIS K 7211 is 4 to 20 J when a cured product is obtained by curing at 140 ° C for 60 minutes and further at 220 ° C for 120 minutes.   A cured product produced from the resin composition according to claim 6 or 7. An addition reaction step of adding an epihalohydrin to a polyol compound represented by the following formula (4) in the presence of a solid acid catalyst to obtain an epihalohydrin ether;
A ring closing reaction step of ring closing the epihalohydrin ether in the presence of an alkaline compound to obtain an epoxy resin;
The manufacturing method of the epoxy resin as described in any one of Claims 1-5.
(In the formula (4), m and n are each independently an integer of 1 or more, and R ¹ and R ² are each independently a divalent aliphatic group having 1 to 12 carbon atoms, or represents a divalent aromatic group having 6 to 40 carbon atoms, at least one of R ¹ and R ² is represented by.-R ¹ O-representing a divalent aromatic group having 6 to 40 carbon atoms The average addition number of units is 5.0 or more and 12.0 or less per molecule of the polyol compound.)