JP2011213831A - Epoxy resin composition including phosphorus-containing curing agent for epoxy resin, cured product thereof, and method for producing the same - Google Patents

Abstract

[PROBLEMS] To provide a novel flame retardant epoxy resin composition using a phosphophenol novolac resin as a curing agent and to cure epoxy resin excellent in flame retardancy, electrical characteristics and water absorption resistance, and to prevent bleeding out of the flame retardant. To provide a product and a method for manufacturing the product.
A phenol novolac resin comprising a bis (methylphenyl) phosphine oxide group in a resin crosslinking group. An epoxy resin composition containing the phenol novolac resin as a curing agent, and a cured product obtained by curing the epoxy resin composition.
[Selection figure] None

Description

  The present invention relates to an epoxy resin composition containing a phosphorus-containing phenol novolac resin as a curing agent for an epoxy resin and a cured product of an epoxy resin obtained by curing the epoxy resin composition. The cured product is suitably used for electrical and electronic industries, for sealing electronic components, and for laminates, and is useful as a cured product having excellent flame retardancy.

  Epoxy resins are often used as resins for electronic materials. For example, Patent Document 1 discloses an epoxy resin composition containing an inorganic filler for use as a semiconductor sealing material such as an underfill agent. Various phenol novolac resins, amines, and acid anhydrides are used as curing agents for epoxy resins used as resins for electronic materials. In particular, a phenol novolac resin is mainly used as a curing agent for an epoxy resin for semiconductor encapsulation in terms of heat resistance and reliability. In recent years, these resins are required to have flame retardancy from the viewpoint of safety aimed at preventing fire due to high temperatures.

  In general, various methods are known for making a resin flame-retardant. As a method for making the resin flame-retardant, it is particularly possible to add a halogen compound. However, it is said that halogen compounds may generate dioxins. Therefore, a non-halogen flame retardant is desired as a flame retardant for resins replacing halogen compounds. Among non-halogen compounds, a high effect is recognized in the addition of organophosphorus compounds, and it has been studied energetically, but simply adding an amount of flame retardant to the resin to achieve the desired flame retardancy Prone to bleeding phenomenon.

  Patent Document 2 discloses a resin composition containing an oligomer in which a phosphate ester structure is incorporated into a skeleton, but the oligomer is weak in hydrolysis resistance, and the cured product of the resin composition has high water absorption. There are drawbacks. Further, Patent Document 3 discloses a flame retardant epoxy resin in which a phosphorus atom is incorporated into a skeleton using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as a raw material. This compound also has a phosphate bond moiety in the molecule, and satisfactory hydrolysis resistance cannot be obtained.

JP 2008-13710 A JP 11-343382 A JP 2000-154234 A

  The object of the present invention is to prevent a novel flame retardant epoxy resin composition using a phosphophenol novolac resin as a curing agent, as well as bleeding out of the flame retardant, and is excellent in flame retardancy, electrical characteristics and water absorption resistance. The object is to provide a cured epoxy resin.

  As a result of repeated investigations to solve the above-mentioned problems, the inventors of the present invention include a novel phenol novolac resin containing a bis (methylphenyl) phosphine oxide structure as a resin crosslinking group as a curing agent. It has been found that this problem can be solved by the epoxy resin composition.

That is, the present invention relates to the general formula (1):

(Where
R ¹ is an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n is 0-9)
It is related with the epoxy resin composition containing the phosphorus containing phenol novolak resin shown by and epoxy resin.
The present invention further relates to the epoxy resin composition as described above, further comprising an inorganic filler.
The present invention relates to a cured epoxy resin obtained by curing the epoxy resin composition described above.
This invention relates to the semiconductor sealing material which consists of an epoxy resin composition as described above.
The present invention relates to a semiconductor device sealed using the semiconductor sealing material described above.
This invention is a manufacturing method of the epoxy resin hardened | cured material as described above, Comprising: It is related with the method including the process of heat-hardening the epoxy resin as described above at the curing temperature of 100-250 degreeC.

  INDUSTRIAL APPLICABILITY According to the present invention, there are provided an epoxy resin that can prevent a bleed-out of a flame retardant and provide a novel epoxy cured product excellent in flame retardancy, and a cured product of an epoxy resin obtained by curing the epoxy resin. be able to.

The chart of the thermogravimetric analysis (TGA) measurement of the epoxy resin hardened | cured material obtained in Example 1 and Reference Example 2 is shown. The chart of the thermogravimetric analysis (TGA) measurement of the cured epoxy resin obtained in Example 2 and Reference Example 3 is shown. The chart of the thermogravimetric analysis (TGA) measurement of the epoxy resin hardened | cured material obtained in Example 3 and Reference Example 4 is shown.

  The epoxy resin composition of this invention contains the phosphorus containing phenol novolak resin shown by General formula (1) as a hardening | curing agent, and an epoxy resin as an essential component.

The phosphorus-containing phenol novolac resin that is a curing agent of the epoxy resin composition of the present invention has the general formula (1):

(Wherein R ¹ , R ² and n are as defined above)
Indicated by

In R ¹ , the alkyl group having 1 to 4 carbon atoms is linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Preferably it is a C1-C4 linear alkyl group, More preferably, it is a methyl group.

In R ¹ , an aryl group having 6 to 10 carbon atoms is an aryl group which may be substituted once or more with an alkyl group having 1 to 4 carbon atoms, but the total number of carbon atoms is 6 to 10 . Examples of the alkyl group having 1 to 4 carbon atoms include the groups defined above including specific examples and preferred groups, and the substitution positions of the alkyl group having 1 to 4 carbon atoms are ortho, meta, and para positions. Either of these may be used. Examples of these groups include phenyl group, toluyl group (2-toluyl group, 3-toluyl group, and 4-toluyl group), and xylyl group (2,3-xylyl group, 2,4-xylyl group, 2,5 -Xylyl group, 2,6-xylyl group, 3,5-xylyl group). The aryl group having 6 to 10 carbon atoms is preferably a phenyl group.

In R ¹ , the aralkyl group having 7 to 11 carbon atoms is an alkyl group having 1 to 4 carbon atoms substituted with an aryl group having 6 to 10 carbon atoms, but the total number of carbon atoms is 7 to 11 is there. Examples of the aryl group having 6 to 10 carbon atoms and the alkyl group having 1 to 4 carbon atoms include the groups defined above including specific examples and preferred groups. Examples of these groups include a benzyl group and a phenylethyl group, with a benzyl group being preferred.

R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms in R ² include groups defined by R ¹ including specific examples and preferred groups. When R ² is an alkyl group having 1 to 4 carbon atoms, the substitution position of R ² may be any of ortho, meta, and para positions.

  In general formula (1), n is 0-9. In order to secure the fluidity of the phosphorus-containing phenol novolak resin represented by the general formula (1), n is preferably 0 to 5. In the present invention, n is calculated based on the weight average molecular weight measured by GPC (gel permeation chromatography) measurement.

From the above, in the phosphorus-containing phenol novolac resin represented by the general formula (1), R ¹ is a phenyl group, R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is What is 0-5 is preferable.

Method for producing phosphorus-containing phenol novolac resin represented by general formula (1) of the present invention In the present invention, the phosphorus-containing phenol novolak resin represented by general formula (1) is represented by the following general formula (2):

(Wherein R ² is as defined in general formula (1))
A phenol compound represented by the general formula (3):

(Where
R ¹ is as defined in the general formula (1),
X ¹ is independently of each other a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a methanesulfonyloxy group, or a toluenesulfonyloxy group.
It can obtain by making it react with the bis (methylphenyl) phosphine oxide compound shown by these.

  In the present invention, the phenolic compound represented by the general formula (2) is a phenol having one phenolic hydroxyl group or a derivative thereof. Examples of the phenol compound represented by the general formula (2) include phenol and cresol, and phenol is more preferable. Such a compound represented by the general formula (2) is generally commercially available.

  The bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is a compound that introduces a structure of a bis (methylphenyl) phosphine oxide crosslinking group that imparts flame retardancy to the phosphorus-containing phenol novolac resin of the present invention. It is.

In the general formula (3), X ¹ are each independently a halogen atom, hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a methanesulfonyloxy group or a toluenesulfonyloxy group.

Examples of the halogen atom in X ¹ include a chlorine atom, a bromine atom, and an iodine atom, and from the viewpoint of high reactivity, a chlorine atom or a bromine atom is preferable.

Examples of the alkoxy group having 1 to 4 carbon atoms in X ¹ include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group, and a methoxy group is preferable from the viewpoint of high reactivity.

In the general formula (3), X ¹ is preferably the same and is a halogen atom or an alkoxy group having 1 to 4 carbon atoms.

  Accordingly, the bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is preferably phenylbis (4-bromomethylphenyl) phosphine oxide and phenylbis (4-methoxymethylphenyl) phosphine oxide.

  The bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is composed of phosphorus and aromatics by a Grineer reaction between a dichlorophosphine compound and a Grineer reagent or a Friedel-Crafts reaction between a dichlorophosphine compound and toluene It is obtained by a production method using bond formation with a carbon atom, and a method including a step of forming a bond between a phosphorus atom and a sulfur atom or oxygen atom.

(I) Method for producing bis (methylphenyl) phosphine oxide compound represented by general formula (3) using Grineer reaction Bis (methylphenyl) phosphine represented by General Formula (3) using Grineer reaction of the present invention The method for producing an oxide compound includes the following steps (1A) to (1C):
(1A) General formula (3a):

(Where
R ¹ is as defined in the general formula (1),
m is 0 or 1,
A is an oxygen atom or a sulfur atom,
X ² is an alkoxy group having 1 to 4 carbon atoms)
A bis (alkoxymethylphenyl) phosphine compound represented by the general formula (4):

(Where
R ¹ is as defined in the general formula (1),
m and A are as defined in general formula (3a))
A dichlorophosphine compound represented by the general formula (5):

(Where
X ² is as defined in general formula (3a),
B is a halogen atom)
A step of obtaining a bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) by reacting with a Grineer reagent represented by:
(1B) In addition, the general formula X ² bis (alkoxymethyl phenyl) phosphine compound represented by (3a), X ¹ is substituted with groups other than alkoxy groups having 1 to 4 carbon atoms, the general formula ( 3b):

(Where
R ¹ is as defined in the general formula (1),
m and A are as defined in the general formula (3a),
X ³ is independently of each other a halogen atom, a hydroxy group, a methanesulfonyloxy group or a toluenesulfonyloxy group)
Obtaining a bifunctional phosphorus-containing compound represented by:
(1C) Furthermore, m is 0, the compound represented by general formula (3a) or (3b), or m is 1, and A is a sulfur atom, and is represented by general formula (3a) or (3b) Converting the compound to a compound represented by the general formula (3a) or (3b), wherein m is 1 and A is an oxygen atom;
Is obtained by a method comprising

(I-1) Step (1A)
The bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) is obtained from a dichlorophosphine compound represented by the general formula (4) and a Grineer reagent represented by the general formula (5). In step (1A), a bond is formed between phosphorus and an aromatic carbon atom.

  The dichlorophosphine compound represented by the general formula (4) is a raw material compound of the bis (methylphenyl) phosphine oxide compound represented by the general formula (3), m is 0, a dichlorophosphine compound, m is 1 And a dichlorophosphine oxide compound in which A is a sulfur atom, m is 1, and A is an oxygen atom.

  Examples of the dichlorophosphine compound include dichlorophenylphosphine, dichloromethylphosphine, dichloroethylphosphine, dichloropropylphosphine, dichloroisopropylphosphine, and dichloro-t-butylphosphine.

  Examples of the dichlorophosphine sulfide compound include dichloromethylphosphine sulfide, dichlorophenylphosphine sulfide, dichloroethylphosphine sulfide, dichloropropylphosphine sulfide, dichloroisopropylphosphine sulfide, and dichloro-t-butylphosphine sulfide. A dichlorophosphine sulfide compound can be obtained by reacting a dichlorophosphine compound with sulfur.

  Examples of the dichlorophosphine oxide compound include dichloromethylphosphine oxide, dichlorophenylphosphine oxide, dichloroethylphosphine oxide, dichloropropylphosphine oxide, dichloroisopropylphosphine oxide, and dichloro-t-butylphosphine oxide.

  Such a dichlorophosphine compound represented by the general formula (4) is commercially available.

In the method for obtaining a bis (methylphenyl) phosphine oxide compound represented by the general formula (3) using the Grineer reaction of the present invention, the general formula (4a):

(Wherein R ¹ is as defined in general formula (1))
The dichlorophosphine compound shown by these is preferable.

  The Grineer reagent represented by the general formula (5) is a raw material compound of a bis (methylphenyl) phosphine oxide compound represented by the general formula (3).

  B in General formula (5) is a halogen atom, for example, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a bromine atom.

X ² in the general formula (5) is an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms in X ² include the same groups as defined in X ¹ .

  The Grineer reagent represented by the general formula (5) can be produced by a known method, and can be obtained, for example, by reacting shaved magnesium with a corresponding halogen-substituted aromatic compound.

  The amount of the Grineer reagent represented by the general formula (5) is preferably 1.0 to 4.0 moles, more preferably 1 mole relative to 1 mole of the dichlorophosphine compound represented by the general formula (4). 2.0 to 3.0 moles.

  In the present invention, the reaction for obtaining the bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) using the Grineer reaction can be performed without a solvent, or can be performed in an organic solvent. it can. Usable organic solvents include ethers such as tetrahydrofuran and dioxane, and linear or cyclic aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane. In addition, these solvents can be used individually or in mixture of 2 or more types. Moreover, the usage-amount of an organic solvent becomes like this. Preferably it is 0-30 mol with respect to 1 mol of dichlorophosphine compounds shown by General formula (4), More preferably, it is 0-10 mol.

  When the compound represented by the general formula (3a) obtained in the step (1A) is a bis (alkoxymethylphenyl) phosphine compound in which m is 0, the method of the present invention is performed after the step (1A), You may have the process of forming the coupling | bonding of phosphorus and a sulfur atom, or the coupling | bonding of phosphorus and an oxygen atom. When the compound represented by the general formula (3a) obtained in the step (1A) is a bis (alkoxymethylphenyl) phosphine sulfide compound in which m is 1 and A is a sulfur atom, the method of the present invention. May have a step of forming a bond between phosphorus and an oxygen atom after the step (1A).

  In the present invention, a bond between phosphorus and a sulfur atom can be formed by reacting sulfur with a bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) in which m is 0. As a result, a bis (alkoxymethylphenyl) phosphine sulfide compound represented by the general formula (3a), wherein m is 1 and A is a sulfur atom, is obtained.

  The amount of sulfur added is preferably 0.5 to 2 mol, more preferably 1. mol, per 1 mol of the bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) in which m is 0. 0 to 1.5 mol.

In the present invention, by reacting a bis (alkoxymethylphenyl) phosphine sulfide compound represented by the general formula (3a), in which m is 1 and A is a sulfur atom, with an oxidizing agent, phosphorus and oxygen atoms are reacted. Can be formed. Thereby, a bis (alkoxymethylphenyl) phosphine oxide compound corresponding to the compound represented by the general formula (3), in which X ¹ is an alkoxy group having 1 to 4 carbon atoms, is obtained.

  As the oxidizing agent, various oxidizing agents can be used, specifically, halogen molecules such as chlorine gas and bromine, halogenating agents such as thionyl chloride, sulfuryl chloride, phosphorus trichloride, and phosphorus tribromide, Examples include peroxides such as hydrogen peroxide, m-chloroperbenzoic acid, and peracetic acid, manganese oxide, and potassium permanganate. As the oxidizing agent, sulfuryl chloride and hydrogen peroxide are preferable.

  The addition amount of the oxidizing agent is preferably 0.5 to 2 with respect to 1 mol of the bis (alkoxymethylphenyl) phosphine sulfide compound represented by the general formula (3a) in which m is 1 and A is a sulfur atom. Mol, more preferably 1.0 to 1.5 mol.

(I-2) Step (1B)
In the step (1B), a bifunctional phosphorus-containing compound represented by the general formula (3b) is obtained.

As a compound represented by the general formula (3a), which is a raw material compound in the step (1B), m is 0, a bis (alkoxymethylphenyl) phosphine compound, m is 1, and A is a sulfur atom. (Alkoxymethylphenyl) phosphine sulfide compounds and bis (alkoxymethylphenyl) phosphine oxide compounds in which m is 1 and A is an oxygen atom. When the compound represented by the general formula (3a), which is a raw material compound, is a bis (alkoxymethylphenyl) phosphine oxide compound in which m is 1 and A is an oxygen atom, in step (1B), X ¹ is A bis (methylphenyl) phosphine oxide compound corresponding to the compound represented by the general formula (3) other than the alkoxy group having 1 to 4 carbon atoms is obtained.

  As these compounds, the compound obtained in the step (1A) may be used as it is, and after the step (1A), it is obtained by a method including a step of forming a bond between phosphorus and a sulfur atom or an oxygen atom. A compound may be used.

The X ^2, a method of X ¹ is substituted to X ³ corresponding to the group other than an alkoxy group having from 1 to 4 carbon atoms, for example the following method can be mentioned.

  By reacting the bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) with a halogenating agent such as thionyl chloride, an alkoxy group having 1 to 4 carbon atoms can be substituted with a halogen atom. .

A halogen atom is converted to a carbon atom by reacting a bifunctional phosphorus-containing compound represented by the general formula (3b) wherein X ³ is a halogen atom with an alkali metal alkoxide having 1 to 4 carbon atoms, such as sodium methoxide. It can be substituted with an alkoxy group of formulas 1-4.

A halogen atom is substituted with an acyloxy group by reacting a bifunctional phosphorus-containing compound represented by the general formula (3b) wherein X ³ is a halogen atom with an alkali metal alkylcarboxylate such as potassium acetate, By reacting with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to replace the acyloxy group with a hydroxy group, the halogen atom can be replaced with a hydroxy group.

A hydroxy group can be substituted with a p-toluenesulfonyloxy group by reacting a bifunctional phosphorus-containing compound represented by the general formula (3b) where X ³ is a hydroxy group with p-toluenesulfonyl chloride. Moreover, a hydroxy group can be substituted with a methanesulfonyloxy group by reacting with methanesulfonyl chloride.

(I-3) Step (1C)
In step (1C), m is 1 and A is an oxygen atom. A bis (alkoxymethylphenyl) phosphine compound represented by the general formula (3a) or a bifunctional phosphorus-containing compound represented by (3b), A bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is obtained. The starting compound in the step (1C) is a bis (alkoxymethylphenyl) phosphine compound corresponding to the compound represented by the general formula (3a) in which m is 0, m is 1, and A is a sulfur atom. Bis (alkoxymethylphenyl) phosphine sulfide compound corresponding to the compound represented by the general formula (3a), bis (methylphenyl) phosphine compound corresponding to the compound represented by the general formula (3b) wherein m is 0, And m is 1, and A is a sulfur atom, and a bis (methylphenyl) phosphine sulfide compound corresponding to the compound represented by the general formula (3b) is exemplified.

  In the present invention, in the case of a bis (methylphenyl) phosphine compound corresponding to the compound represented by the general formula (3a) or the general formula (3b) in which m is 0, the step (1C) includes phosphorus and a sulfur atom. And a step of forming a bond between phosphorus and an oxygen atom. In the case where the compound is a bis (methylphenyl) phosphine sulfide compound corresponding to the compound represented by the general formula (3a) or the general formula (3b), wherein m is 1 and A is a sulfur atom, the step (1C) Includes a step of forming a bond between phosphorus and an oxygen atom. Examples of such a step include those exemplified in the step (1A).

(II) Method for producing bis (methylphenyl) phosphine oxide compound represented by general formula (5) using Friedel-Crafts type reaction In the present invention, it is represented by General Formula (5) using Friedel-Crafts type reaction The bifunctional phosphorus-containing compound includes the following steps (2A) to (2D):
(2A) General formula (4):

(Where
R ¹ is as defined in the general formula (1),
m and A are as defined in general formula (3a))
Is reacted with toluene and the general formula (6):

(Where
R ¹ is as defined in the general formula (1),
m and A are as defined in general formula (3a))
A step of obtaining a bis (methylphenyl) phosphine compound represented by:
(2B) By reacting a bis (methylphenyl) phosphine compound represented by the general formula (6) with a halogenating agent containing X ⁴ , the general formula (3f):

(Where
R ¹ is as defined in the general formula (1),
m and A are as defined in the general formula (3a),
X ⁴ is a halogen atom)
A step of obtaining a bis (halogenomethylphenyl) phosphine compound represented by:
(2C) Further, X ⁴ of the bis (halogenomethylphenyl) phosphine compound represented by the general formula (3f) is substituted with X ⁵ corresponding to X ¹ other than a halogen atom, thereby obtaining the general formula (3g):

(Where
R ¹ is as defined in the general formula (1),
m and A are as defined in the general formula (3a),
X ⁵ is independently of each other a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a methanesulfonyloxy group or a toluenesulfonyloxy group)
Obtaining a bifunctional phosphorus-containing compound represented by:
(2D) Further, a compound represented by the general formula (3f) or (3g) in which m is 0, or represented by the general formula (3f) or (3g) in which m is 1 and A is a sulfur atom. Converting the compound to a compound represented by the general formula (3f) or (3g), wherein m is 1 and A is an oxygen atom;
Is obtained by a method comprising

(II-1) Step (2A)
The bis (methylphenyl) phosphine compound represented by the general formula (6) of the present invention is obtained from the dichlorophosphine compound represented by the general formula (4) and toluene. In step (2A), a bond is formed between phosphorus and the aromatic carbon atom.

  In the present invention, examples of the dichlorophosphine compound represented by the general formula (4) used in the step (2A) include the same compounds as those that can be used in the Grineer reaction. When a catalyst is used for the Friedel-Crafts reaction, the reaction proceeds with a small amount of the catalyst. Therefore, the dichlorophosphine compound or the dichlorophosphine sulfide compound represented by the general formula (4a) is preferable. Similar compounds are more preferred.

  In the step (2A), the amount of toluene used as a raw material is preferably 2 to 30 mol and more preferably 2 to 10 mol with respect to 1 mol of the dichlorophosphine compound represented by the general formula (4).

  In step (2A), a catalyst can be used to accelerate the reaction. Examples of the catalyst include Lewis acid catalysts used in the Friedel-Crafts reaction for carbon-carbon bond formation. Specifically, aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin chloride (II ), Titanium tetrachloride, bismuth chloride, bismuth triflate, yttrium triflate, and the like. 0.1-3 mol is preferable with respect to 1 mol of dichlorophosphine compounds shown by General formula (4) which is a raw material, and, as for the usage-amount of the said catalyst, 0.5-2 mol is more preferable.

  When the compound represented by the formula (6) obtained in the step (2A) is a bis (methylphenyl) phosphine compound in which m is 0, the method of the present invention can be carried out after the step (2A) with phosphorus You may have the process of forming the coupling | bonding with a sulfur atom, or the coupling | bonding of phosphorus and an oxygen atom. When the compound represented by the formula (6) obtained in the step (2A) is a bis (methylphenyl) phosphine sulfide compound in which m is 1 and A is a sulfur atom, You may have the process of forming the coupling | bonding of phosphorus and an oxygen atom after a process (2A). Examples of such a step include those exemplified in the step (1A). Further, when the dichlorophosphine compound represented by the general formula (4a) is used as a raw material, a bond between phosphorus and a sulfur atom and a bond between phosphorus and toluene can be introduced in one step. Therefore, as the step (2A), By reacting the dichlorophosphine compound represented by the general formula (4), toluene, and sulfur, m is 1, and A is a sulfur atom. The bis (methylphenyl) represented by the general formula (6) A step of obtaining a phosphine sulfide compound is preferred.

(II-2) Step (2B)
In the step (2B), the bis (halogenomethylphenyl) phosphine compound represented by the general formula (3f) of the present invention is a bis (methylphenyl) phosphine compound represented by the general formula (6) and a halogen containing X ^4. Obtained from an agent.

As the bis (methylphenyl) phosphine compound represented by the general formula (6), m is 0, bis (methylphenyl) phosphine compound, m is 1, and A is a sulfur atom, bis (methylphenyl) Examples thereof include phosphine sulfide compounds and bis (methylphenyl) phosphine oxide compounds in which m is 1 and A is an oxygen atom. When the compound represented by the general formula (6) is a bis (methylphenyl) phosphine oxide compound in which m is 1 and A is an oxygen atom, in step (2B), X ¹ is a halogen atom A bis (methylphenyl) phosphine oxide compound corresponding to the compound represented by the general formula (3) is obtained.

  As the compound represented by the general formula (6), the compound obtained in the step (2A) may be used as it is, and a step of forming a bond between phosphorus and a sulfur atom or an oxygen atom after the step (2A). You may use the compound obtained by the method containing this. Preferably, in the step (2A), m is 1 obtained by reacting the dichlorophosphine compound represented by the general formula (4a), toluene, and sulfur, and A is a sulfur atom. A bis (methylphenyl) phosphine sulfide compound represented by (6).

The halogenating agent containing X ⁴ used in the step (2B) is not particularly limited, and N-chlorosuccinimide, N-bromosuccinimide, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus tribromide, oxychloride Examples thereof include phosphorus, chlorine, bromine, alkali metal hypochlorite, alkali metal hypobromite, and cyanuric chloride. In the present invention, halogenating agents such as halogen molecules, thionyl chloride, sulfuryl chloride, phosphorus trichloride and phosphorus tribromide can be used as oxidizing agents. When a halogenating agent that can be used as an oxidizing agent is used, both an oxidation reaction and a halogenation can be performed, but the oxidation reaction occurs preferentially.

  Therefore, the usage-amount of a halogenating agent becomes like this. Preferably it is 2.0-10.0 mol with respect to 1 mol of bis (methylphenyl) phosphine compounds shown by General formula (6), More preferably, 2. 0 to 5.0 mol. The halogenating agent that can also be used as an oxidizing agent is a bis represented by the general formula (6) in which m is 1 and A is a sulfur atom for both halogenation and oxidation reactions. Preferably it is 3.0-10.0 mol with respect to 1 mol of (methylphenyl) phosphine sulfide compounds, More preferably, it is 3.0-5.0 mol. With such a use amount, halogenation and formation of a bond between phosphorus and an oxygen atom can be performed in one step.

  The reaction for the production method of the bis (halogenomethylphenyl) phosphine compound represented by the general formula (3f) including the steps (2A) to (2B) can be performed without a solvent, or in an organic solvent. Can also be done. Any organic solvent that does not participate in the reaction can be used as the organic solvent. Specifically, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; tetrahydrofuran And chain or cyclic aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; and nitrated compounds such as nitromethane, nitroethane, and nitrobenzene; Mention may be made of organic solvents. In addition, these organic solvents can be used individually or in mixture of 2 or more types. The amount of the organic solvent used is preferably 0 to 30 mol, more preferably 0 to 10 mol, relative to 1 mol of the dichlorophosphine compound represented by the general formula (4) as the raw material.

(II-3) Step (2C)
In the step (2C), the compound represented by the general formula (3g) is represented by the following formula. X ⁴ of the bis (halogenomethylphenyl) phosphine compound represented by the general formula (3f) is represented by X ^{5 wherein} X ¹ is other than a halogen atom. It is obtained by the method including the process of substituting. When the compound represented by the general formula (3f), which is a raw material compound in the step (2C), is a bis (halogenomethylphenyl) phosphine oxide compound in which m is 1 and A is an oxygen atom, the step (2C) Thus, a bis (methylphenyl) phosphine oxide compound corresponding to the compound represented by the general formula (3), wherein X ¹ is other than a halogen atom, is obtained.

A method of substituting X ⁴ of the bis (halogenomethylphenyl) phosphine compound represented by the general formula (3f) with X ⁵ corresponding to a group in which X ¹ is other than a halogen atom is exemplified in Step (1B). Method.

(II-4) Step (2D)
In step (2D), m is 1, and A is an oxygen atom. A bis (halogenomethylphenyl) phosphine compound represented by formula (3f) or a bifunctional phosphorus-containing compound represented by (3g), A bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is obtained. The starting compound in the step (2D) is a bis (halogenomethylphenyl) phosphine compound corresponding to the compound represented by the general formula (3f) in which m is 0, m is 1, and A is a sulfur atom. Bis (halogenomethylphenyl) phosphine sulfide compound corresponding to the compound represented by the general formula (3f), bis (methylphenyl) phosphine compound corresponding to the compound represented by the general formula (3g) wherein m is 0, And m is 1, A is a sulfur atom, and a bis (methylphenyl) phosphine sulfide compound corresponding to the compound represented by the general formula (3g) is exemplified.

  In the present invention, in the case of a bis (methylphenyl) phosphine compound corresponding to the compound represented by the general formula (3f) or the general formula (3g) in which m is 0, the step (2D) includes phosphorus and a sulfur atom. And a step of forming a bond between phosphorus and an oxygen atom. When m is 1 and A is a sulfur atom, a bis (methylphenyl) phosphine sulfide compound corresponding to the compound represented by formula (3f) or (3g), step (2D) Includes a step of forming a bond between phosphorus and an oxygen atom. Examples of such a method include those exemplified in the step (1A).

As described above, in the method for producing a bis (methylphenyl) phosphine oxide compound represented by the general formula (3) using a Friedel-Crafts-type reaction, the bis (methylphenyl) phosphine oxide compound represented by the general formula (3) Is preferably steps (3A) to (3D):
(3A) General formula (4a):

Wherein R ¹ is as defined above.
Is reacted with toluene in the presence of sulfur to give a general formula (6a):

(Wherein R ¹ is as defined in general formula (1))
A step of obtaining a bis (methylphenyl) phosphine sulfide compound represented by:
(3B) The bis (methylphenyl) phosphine sulfide compound obtained in step (3A) is reacted with an oxidizing agent to give a general formula (6b):

(Wherein R ¹ is as defined in general formula (1))
Obtaining a bis (methylphenyl) phosphine oxide compound;
(3C) Bis (methylphenyl) represented by the general formula (3) in which X ¹ is halogen by reacting the bis (methylphenyl) phosphine oxide compound obtained in step (3B) with a halogenating agent. General formula (3i) corresponding to phosphine oxide compounds:

(Where
R ¹ is as defined in the general formula (1),
X ⁴ is as defined in general formula (3f))
Obtaining a bis (halogenomethylphenyl) phosphine oxide compound represented by:
(3D) Further obtained by a method comprising the step of substituting X ⁴ of the bis (halogenomethylphenyl) phosphine oxide compound obtained in step (3C) with X ⁵ where X ¹ corresponds to a group other than a halogen atom. It is done.

  In the present invention, the phenol represented by the general formula (4) is reacted with the bis (methylphenyl) phosphine oxide compound represented by the general formula (3) to react with the phenol represented by the general formula (4). A bond is formed between the aromatic carbon atom of the similar compound and the bis (methylphenyl) phosphine-based bridging group.

  In the present invention, the molar ratio of the phenol compound represented by the general formula (2) and the bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is 1.2: 1 to 30: 1. It is preferably 1.2: 1 to 10: 1, more preferably 5: 1 to 10: 1.

  In the present invention, the reaction temperature in the reaction of the phenol compound represented by the general formula (2) and the bis (methylphenyl) phosphine oxide compound represented by the general formula (3) is preferably 50 to 180 ° C. More preferably, it is 100-150 degreeC. The reaction time is affected by the reaction temperature, but is usually within 24 hours.

  In the present invention, when the phenol compound represented by the general formula (2) is reacted with the bis (methylphenyl) phosphine oxide compound represented by the general formula (3), an acid is used to smoothly advance the reaction. A catalyst may be used.

  Examples of the acid catalyst to be used include oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid and the like, preferably oxalic acid and hydrochloric acid. The amount of the acid catalyst used is preferably 0 to 0.01 mol with respect to the phenol compound represented by the general formula (2) which is a raw material compound.

The epoxy resin in the epoxy resin composition of the present invention is not particularly limited as long as it is a compound having an average of 2 or more epoxy groups per molecule.
Examples of the epoxy resin include phenols such as phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β- A novolak epoxy obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst. Resin; bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 3,3 ′, 5,5′-tetramethyl- (1,1′-biphenyl)- 4,4'-diol diglycidyl ether, alkyl-substituted or unsubstituted biphenol, diglycidyl ethers such as stilbene phenols (bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin); 1,4-butanediol Aliphatic glycidyl ethers such as diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether; glycidyl esters such as glycidyl phthalate and glycidyl hexahydrophthalate; aniline, Glycidyl-type or methylglycidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as isocyanuric acid is substituted with a glycidyl group; obtained by epoxidizing olefin bonds in the molecule Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, limonene Cycloaliphatic epoxy compounds such as dioxide, allyl cyclohexylene dioxide, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexyl) ether; glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin; Glycidyl ether of terpene modified phenolic resin; Glycidyl ether of dicyclopentadiene modified phenolic resin; Glycidyl ether of cyclopentadiene modified phenolic resin; Glycidyl ether of aromatic ring-modified phenol resin; Glycidyl ether of phenol resin containing naphthalene ring; Halogenated phenol novolac type epoxy resin; Hydroquinone type epoxy resin; Trimethylolpropane type epoxy resin; Oxidized olefin bond with peracid such as peracetic acid Linear aliphatic epoxy resin obtained; diphenylmethane type epoxy resin; epoxidized aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin; sulfur atom-containing epoxy resin; naphthalene type epoxy resin; and epoxidized polybutadiene, epoxidized Epoxidized polydiene compounds obtained by epoxidizing a compound having a diene structure such as polyisoprene; and the like can be used alone or in combination of two or more It may be used.

In the present invention, the novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but novolak type phenol resins such as phenol novolak, cresol novolak, naphthol novolak, etc. Epoxy resins epoxidized using a method such as sidyl etherification are preferred. For example, the general formula (7):

(Where
R ³ and R ⁴ are each independently a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms,
i is an integer of 0 to 3,
n is a number from 0 to 10)
An epoxy resin represented by is more preferable.

Specific examples of the monovalent organic group having 1 to 18 carbon atoms and preferable examples of R ³ and R ⁴ include groups defined by R ¹ . Among them, epoxy resins represented by the general formula (7) in which R ³ is a hydrogen atom, R ⁴ is a methyl group, and i is 1 are ESCN-190 and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.). ) Etc. are available as commercial products.

In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the phosphorus-containing phenol novolac resin represented by the general formula (1) of the present invention as a curing agent for the epoxy resin is the total number of epoxy groups and epoxy in the epoxy resin. The ratio of the total number of phenolic hydroxyl groups of the phosphorus-containing phenol novolak resin represented by the general formula (1) of the present invention as a curing agent for resins, that is, the total number of epoxy groups / total number of phenolic hydroxyl groups is 0.5 to 2. Is preferably 0.0, more preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3. When the blending ratio exceeds 2.0, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to decrease. On the other hand, if the blending ratio is less than 0.5, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are lowered. Tend to.

  In the epoxy resin composition containing the phosphorus-containing phenol novolac resin of the present invention, additives such as an inorganic filler, a curing accelerator, a release agent, a colorant, and a low stress agent are added to the extent that the object of the present invention is not impaired. Can be included.

  The epoxy resin composition of the present invention can further contain an inorganic filler. In particular, when the epoxy resin composition of the present invention is used as a semiconductor encapsulant, the epoxy resin composition of the present invention contains a phosphorus-containing phenol novolac resin represented by the general formula (1), an epoxy resin, and an inorganic filler. Including wood.

  Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia, and barium sulfate. In the present invention, amorphous silica, crystalline silica, and the like are particularly preferable because the thermal expansion coefficient of the encapsulant can be reduced, thereby improving the connection reliability of the encapsulant.

  The content of the inorganic filler is not particularly limited as long as it is the same as the amount of the inorganic filler used in the epoxy resin composition for semiconductor encapsulation, and may be 80% by weight or less of the epoxy resin composition of the present invention. Preferably, 10 to 70% by weight is more preferable. With such a content, moisture resistance is good, workability is excellent, and connection reliability can be improved.

  In the present invention, a curing accelerator may be further included to accelerate the curing reaction of the epoxy resin. As a hardening accelerator, the well-known hardening accelerator for hardening an epoxy resin with a phenol type hardening | curing agent can be used. Curing accelerators include organic phosphine compounds such as triphenylphosphine and methyldiphenylphosphine and boron salts thereof; tertiary amines such as tributylamine and benzyldimethylamine; quaternary ammonium salts; 2-undecylimidazole; Imidazoles such as ethyl-4-methylimidazole and diazabicycloalkenes and derivatives thereof such as 1,8-diazabicyclo (5,4,0) undecene-7 and tetraphenylboron salts thereof; tetraphenylphosphonium tetraphenylborate; Tetraphenylphosphonium tetrabenzoate borate, tetraphenylphosphonium tetranaphthoic acid borate, tetraphenylphosphonium tetranaphthoyloxyborate, tetraphenylphosphonium tetranaphthyloxy Adducts and the like of a phosphine compound and a quinone compound; tetra-substituted phosphonium tetra-substituted borate such as rate.

  Examples of adducts of phosphine compounds and quinone compounds include phosphine compounds such as triphenylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, and tributylphosphine, and 1,4-benzoquinone, methyl-1 , 4-benzoquinone, methoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and adducts with quinone compounds such as 1,4-naphthoquinone.

  A hardening accelerator may be used independently and may be used in combination of 2 or more type. Among these, 2-undecylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, and 1,8-diazabicyclo (5,4,0) -7-undecene are preferable from the viewpoint of curability and moisture resistance.

  In this invention, the usage-amount of a hardening accelerator has a preferable 0.1-2 weight part with respect to 100 weight part of epoxy resin content.

  A solvent can be added to the epoxy resin composition of the present invention in order to facilitate handling. Such a solvent is not particularly limited as long as it is a solvent that volatilizes during the heat curing of the epoxy resin composition of the present invention. For example, aliphatic ketones such as acetone and methyl ethyl ketone, and acetate esters such as ethyl acetate and butyl acetate. , Aromatic hydrocarbons such as toluene and xylene, and aprotic polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The addition amount of a solvent changes according to the viscosity of the solid content of the epoxy resin composition of this invention, and the hardening method, for example, can be 5-1000 weight part with respect to 100 weight part of solid content.

  In this invention, the hardened | cured material of the epoxy resin composition of this invention is obtained by heat-hardening the epoxy resin composition containing the phosphorus containing phenol novolak resin shown by General formula (1) of this invention.

  In the manufacturing method of the hardened | cured material of the epoxy resin composition of this invention, the epoxy resin composition containing the phosphorus containing phenol novolak resin shown by General formula (1), an epoxy resin, and a hardening accelerator as an epoxy resin composition of this invention. It is preferable to use a product.

  In the present invention, the epoxy resin composition can be molded into a desired shape and cured by heating. For example, the epoxy resin composition can be applied to various substrates such as a metal foil and a release film and cured by heating, and poured into a mold. And heat curing. In the present invention, the cured product obtained by curing the epoxy resin composition is preferably applied onto various substrates and molded into a film shape in order to reduce the generation of bubbles during curing.

  In the present invention, the curing temperature is usually 100 to 250 ° C. In the present invention, the process for heat curing may be performed in one stage or in multiple stages. In order to remove volatile components out of the system, it is preferable to cure at a multi-stage curing temperature. Thereby, the curing temperature can be kept relatively low. For example, the method for producing a cured product of the epoxy resin composition of the present invention includes a step of heat curing the epoxy resin composition of the present invention at a first curing temperature of 100 to 140 ° C, and 140 ° C to 180 ° C. And a step of heat-curing at a second curing temperature that is higher than the first curing temperature.

  Since the curing agent of the phosphorus-containing phenol novolak resin represented by the general formula (1) of the present invention has a bis (methylphenylphosphine oxide) cross-linked structure, it has hydrolysis resistance, and is used as an epoxy resin and a cured product thereof. In contrast, flame retardancy can be imparted. Thereby, the addition amount of a flame retardant can be suppressed. Therefore, the epoxy resin composition containing the phosphorus-containing phenol novolac resin represented by the general formula (1) of the present invention as a curing agent is a resin excellent in flame retardancy and water absorption resistance, and the cured product is difficult to be cured. It can be used as a semiconductor encapsulant for LEDs and the like because it can prevent bleeding out of the flame retardant and is excellent in flame resistance and moisture absorption resistance.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Reference Example 1 Production of phosphorus-containing phenol novolak resin (1-1) Synthesis of phenylbis (4-bromomethylphenyl) phosphine oxide 150 g of toluene was placed in a three-necked flask, 40 g of anhydrous aluminum and 9.6 g of sulfur powder were added, To the suspension, 53.7 g of phenyldichlorophosphine was gradually added dropwise while maintaining the temperature at 40 ° C. or lower. The internal temperature was raised to 110 ° C. over 2 hours after the dropwise addition, and the mixture was stirred for 5 hours while maintaining the temperature. The reaction solution was cooled to room temperature and poured into 300 g of ice at a time while stirring vigorously. The precipitate was separated by filtration, and the filtrate was separated and washed twice with 150 mL of water. 30 g of anhydrous sodium sulfate was added and dried, and the organic layer was concentrated under reduced pressure to obtain 87 g of crude crystals of phenylbis (4-toluyl) phosphine sulfide. The crude crystals were recrystallized with 300 g of methanol to obtain 65 g of white crystals.

  77 g of the phenylbis (4-toluyl) phosphine sulfide was dissolved in 200 mL of chlorobenzene, and 33 g of sulfuryl chloride was gradually added dropwise while maintaining the temperature at 20 ° C. or lower by water cooling. After dropping, the mixture was stirred at room temperature for 1 hour. The mixture was cooled again with water, and 100 g of water was gradually added. After removing the yellow viscous material, liquid separation was performed to obtain an organic layer. It was washed with 150 mL of a 5% aqueous sodium hydrogen carbonate solution, dried by adding 30 g of anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure to obtain 65 g of white crystals of phenylbis (4-toluyl) phosphine oxide.

  65 g of the phenylbis (4-toluyl) phosphine oxide was dissolved in 300 mL of chlorobenzene, 77 g of N-bromosuccinimide and 0.5 g of benzoyl peroxide were sequentially added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling to room temperature, the reaction solution was washed successively with 150 mL of 10% aqueous sodium thiosulfate solution and 150 mL of 5% aqueous sodium hydrogen carbonate solution, and then dried by adding 30 g of anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography (filler; Wako Gel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), developing solvent; toluene / ethyl acetate = 4/1 to 1/1 (volume ratio). )) To obtain 62 g of phenylbis (4-bromomethylphenyl) phosphine oxide as a slightly brown viscous liquid.

(Reference Example 1-2) Synthesis of Phosphorus-Containing Phenol Novolak Resin After putting 19.2 g of phenol and 9.5 g of phenylbis (4-bromomethylphenyl) phosphine oxide into a three-necked flask and reacting at 120 ° C. for 5 hours. The solution was cooled to 90 ° C. and washed twice with 10 g of water to remove acid radicals as much as possible. Unreacted phenol was removed from the organic layer under reduced pressure. The melting point of the obtained resin was 116 to 125 ° C. The average (weight average) of n was 0.3.

Example 1
0.53 g of dimethylacetamide was added to and dissolved in 0.27 g of the phosphorus-containing phenol novolak resin obtained in Reference Example 1 and 0.53 g of 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate. . Further, 0.0053 g of 2-undecylimidazole was added, and the uniform solution was heated in an oven at 160 ° C. for 7 hours to obtain a film-like cured product.

Reference example 2
Phenol novolac resin (Maywa Kasei HF-1: softening point 84 ° C., hydroxyl equivalent 106) 1.00 g, 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate 1.18 g and dimethylacetamide 00 g was added and dissolved. Further, 0.0016 g of 2-undecylimidazole was added, and the uniform solution was heated in an oven at 160 ° C. for 7 hours to obtain a film-like cured product.

Example 2
A mixed liquid was prepared by dissolving 1.03 g of the phenol novolac resin obtained in Reference Example 1 and 0.0106 g of 2-undecylimidazole in 1.02 g of dimethylacetamide. 0.405 g of epoxidized polybutadiene (PB3600 manufactured by Daicel Chemical Industries, Ltd., molecular weight 5900 (number average molecular weight)) was added to 1.02 g of this mixed solution, and the uniform solution was heated in an oven at 120 ° C. for 3 hours. Heated in an oven at 0 ° C. for 9 hours to obtain a film-like cured product.

Reference example 3
1.50 g of phenol novolac resin (Maywa Kasei HF-1: softening point 84 ° C., hydroxyl equivalent 106) and 0.0147 g of 2-undecylimidazole were dissolved in 1.50 g of dimethylacetamide to prepare a mixed solution. 0.94 g of epoxidized polybutadiene (PB3600 manufactured by Daicel Chemical Industries, Ltd .: molecular weight 5900 (number average)) was added to 1.00 g of this mixed solution, and the uniform solution was heated in an oven at 160 ° C. for 7 hours to form a film-like product. A cured product was obtained.

Example 3
1.10 g of phenol novolac resin obtained in Reference Example 1 and 0.0121 g of 2-undecylimidazole were dissolved in 1.10 g of dimethylacetamide to prepare a mixed solution. 0.39 g of 2,2-bis (4-glycidyloxyphenyl) propane was added to 1.00 g of this mixed solution, and the uniform solution was heated in an oven at 160 ° C. for 8 hours to obtain a film-like cured product. .

Reference example 4
1.50 g of phenol novolac resin (Maywa Kasei HF-1: softening point 84 ° C., hydroxyl equivalent 106) and 0.0147 g of 2-undecylimidazole were dissolved in 1.50 g of dimethylacetamide to prepare a mixed solution. 0.43 g of 2,2-bis (4-glycidyloxyphenyl) propane was added to 1.00 g of this mixed solution, and the uniform solution was heated in an oven at 160 ° C. for 6 hours to obtain a film-like cured product. .

Flame retardant test example 1
About 10 mg of the cured product obtained in Example 1 was taken and accurately weighed, and thermogravimetric analysis (TGA) measurement was performed with TG / DTA320 (manufactured by Seiko Denshi Kogyo). For the cured products obtained in Examples 2 and 3 and Reference Examples 2, 3 and 4, thermogravimetric analysis measurements were performed in the same manner.

  The result about the hardened | cured material of Example 1 and Reference Example 2 was shown by overwriting in FIG. Regarding the mass residual amount from 400 ° C. to 800 ° C., the cured product of Example 1 containing phosphorus in the skeleton exceeds the cured product of Reference Example 2, and the amount of char (carbide) formed is larger and more difficult. It was suggested that it is excellent in flammability.

  Although the result about the hardened | cured material of Example 2 and Reference Example 3 was shown by overwriting in FIG. 2, it became the same result.

  The results for the cured products of Example 3 and Reference Example 4 are shown in FIG. Regarding the mass residual amount from 500 ° C. to 800 ° C., the cured product of Example 3 containing phosphorus in the skeleton exceeds the cured product of Reference Example 4, and the amount of char formation is larger, making it more flame retardant. Suggested to be excellent.

  The epoxy resin composition of the present invention can prevent bleed-out of a flame retardant and provides a novel epoxy cured product having excellent flame retardancy. The cured product of the present invention is suitably used for the electrical and electronic industries, for sealing electronic components, and for laminated plates, and is useful as a cured product having excellent flame retardancy.

Claims (6)

General formula (1):

(Where
R ¹ is an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n is 0-9)
The epoxy resin composition containing the phosphorus containing phenol novolak resin shown by and epoxy resin.   Furthermore, the epoxy resin composition of Claim 1 containing an inorganic filler.   A cured epoxy resin obtained by curing the epoxy resin composition according to claim 1.   The semiconductor sealing material which consists of an epoxy resin composition of Claim 2.   A semiconductor device sealed using the semiconductor sealing material according to claim 4.   It is a manufacturing method of the epoxy resin hardened | cured material of Claim 3, Comprising: The method including the process of heat-hardening the epoxy resin of Claim 1 or 2 at the curing temperature of 100-250 degreeC.