TW201605937A - Allyl ether-modified biphenyl aralkyl novolac resin, allyl-modified biphenyl aralkyl novolac resin, method for producing same and composition using same - Google Patents

Abstract

The present invention is an allyl ether-modified biphenyl aralkyl novolac resin represented by general formula (1). (In the formula, each R represents a hydrogen atom or the like, and the R moieties may be the same as or different from each other; each of p, q and r independently represents an integer of 0-3; and n represents a number of 0-20. In this connection, some of the allyl groups in formula (1) may be substituted by hydrogen atoms.)

Description

Allyl ether modified biphenyl aralkyl phenolic resin, allyl modified biphenyl aralkyl phenolic resin, process for producing the same, and composition using the same

The present invention relates to an allyl ether-modified biphenyl aralkyl phenol resin, an allyl-modified biphenyl aralkyl phenol resin, a process for producing the same, and a composition using the same.

a phenolic resin obtained by using a phenol as a raw material monomer, in particular, a bridged phenol resin (also referred to as a phenolic resin) obtained by bridging a phenol with an alkyl group or an aralkyl group, since an epoxy resin composition thereof is usually used. The workability is excellent, and the cured product is excellent in electrical properties, heat resistance, moisture resistance, adhesion, and the like, and thus is widely used in fields such as electrical and electronic parts, structural materials, adhesives, and paints.

In recent years, in the use of electrical and electronic parts and the like, the characteristics of such an epoxy resin composition have been further improved. For example, when it is applied to electronic components related to semiconductors used in more severe environments, electronic components used in display devices using high voltage, large batteries, etc., it is necessary to have both high glass transfer. An epoxy resin composition of a cured product having a temperature and a high flame retardancy. On the other hand, in terms of reducing the environmental load, it is preferable to exhibit a high flame retardancy even though it is halogen-free. However, the epoxy resin composition containing a phenol resin and an epoxy resin has a limit in terms of structural heat resistance obtained, and is not satisfactory.

As a composition exhibiting heat resistance beyond the epoxy resin composition, a composition using an allyl modified phenol compound and a maleimide compound is known. For example, Patent Document 1 discloses a composition excellent in heat resistance by blending diallyl bisphenol A and bismaleimide. Further, in Patent Document 2, it is described that the cyclohexane is reduced by blending. A composition in which the phenolic resin of the alkane bond is obtained by allyl etherification of the allylic ether resin and the bismaleimide to obtain a composition excellent in heat resistance.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 53-134099

Patent Document 2: Japanese Patent Laid-Open No. Hei 8-59533

However, in Patent Documents 1 and 2, no research has been conducted on the flame retardancy, and it has not been proposed to obtain a phenol resin of a maleic imide composition which is not only high in heat resistance but also high in flame retardancy.

Accordingly, an object of the present invention is to provide a phenol resin which is halogen-free but which can be cured by a reaction with a maleimide compound or the like and which has a high glass transition temperature and high flame retardancy. Moreover, an object of the present invention is to provide a method for producing the above phenol resin, a composition containing a maleidinolide compound of the above phenol resin (hereinafter also referred to as a maleimide composition), and a resin composition. Hardened material.

In order to solve the above problems, the present inventors conducted intensive studies and found that an allyl ether-modified biphenyl aralkyl phenol resin obtained by allylation of a specific aralkyl phenol resin and/or Allyl modified biphenyl aralkyl phenolic resin, which can obtain a maleic imine composition and a cured product having high heat resistance and heat resistance which is superior to the heat resistance of the prior epoxy resin cured product. Thus, the present invention has been completed.

That is, the present invention relates to an allyl ether-modified biphenyl aralkyl phenol resin represented by the following formula (1).

(wherein R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different, and p, q and r are each independently Indicates an integer from 0 to 3.

n represents the value of 0~20.

Wherein a part of the allylic groups of the plurality of allyl groups in the formula (1) may be substituted with a hydrogen atom)

Further, the present invention relates to an allyl-modified biphenyl aralkyl phenol resin represented by the following formula (2).

(wherein R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different, and p, q and r are each independently Indicates an integer from 0 to 3.

n represents the value of 0~20.

Wherein a part of the allylic groups of the plurality of allyl groups in the formula (2) may be substituted with a hydrogen atom)

Moreover, the present invention provides a process for producing an allyl ether-modified biphenyl aralkyl phenol resin represented by the above formula (1), which is an aralkyl phenolic resin represented by the following formula (I) The lipid reacts with the allyl halide in the presence of a basic catalyst.

(wherein R, p, q, r and n are the same as in the formula (1))

Moreover, the present invention provides a process for producing an allyl-modified biphenyl aralkyl phenol resin represented by the above formula (2), which is characterized in that the allyl ether represented by the above formula (1) is modified. The phenylaralkyl phenolic resin is subjected to a Claisen rearrangement.

Further, the present invention provides a composition and a cured product thereof comprising the above allyl ether-modified biphenyl aralkyl phenol resin and/or the above allyl modified biphenyl aralkyl phenol resin and one molecule A compound having two or more maleimine groups. Moreover, the present invention provides a sealing material, a semiconductor device, and a printed wiring board material of a semiconductor element containing the above resin or the above composition.

According to the present invention, it is possible to provide a phenol resin which is halogen-free but which can be cured by a reaction with a maleimide compound or the like and which has a high glass transition temperature and high flame retardancy. Further, a method for producing the phenol resin, a maleidene composition comprising the phenol resin, a semiconductor sealing material comprising the maleimide resin composition, and a hardening of the maleimide composition may be provided. And a semiconductor device including the cured product described above. The phenol resin of the present invention can provide a cured product having very good heat resistance or flame retardancy, even in an extremely severe environment which cannot be dealt with by an epoxy resin composition and a cured product containing an epoxy resin or a phenol resin. Since it can be preferably used, it is suitable for electronic components related to automotive semiconductors, electronic components used in display devices using high voltage, large batteries, and the like, and has high industrial applicability.

Fig. 1 is an IR spectrum of a resin represented by the formula (I) used in the examples.

Fig. 2 is an IR spectrum of the resin of Example 1 represented by the formula (1).

Fig. 3 is an IR spectrum of the resin of Example 2 represented by the formula (2).

Hereinafter, the present invention will be described based on preferred embodiments thereof.

The present invention relates to an allyl ether-modified biphenyl aralkyl phenol resin represented by the above formula (1) (hereinafter also referred to as a resin represented by the formula (1) of the present invention) and the above formula ( 2) The allyl-modified biphenyl aralkyl phenol resin (hereinafter, also referred to as the resin represented by the general formula (2) of the present invention). Hereinafter, these resins are also collectively referred to as the resin of the present invention.

The resin of the present invention has a chemical structure in which an allyl group is added to a biphenyl aralkyl phenol resin obtained by bridging a phenol with a phenyl group. The substitution position of the allyl group may be added to the phenolic hydroxyl group in the above biphenyl aralkyl resin by an ether bond in the form of an allyl ether group, or may be added to a biphenyl aralkyl resin. The phenolic monomer is on the benzene ring.

One of the plurality of allyl groups in the above formula (1) and formula (2) may be substituted with a hydrogen atom. For example, the resin represented by the formula (1) of the present invention may not have all of the phenolic hydroxyallyl etherified in the resin, and may have a hydroxyl group which is not etherified.

Specifically, in the general formula (1), although the allyl ether group is bonded to each phenol monomer portion in the resin represented by the general formula (1), the resin of the present invention is also included only in the resin. A phenolic monomer moiety having a non-bonded allyl ether group is bonded to the phenolic monomer moiety of a part of each phenol monomer moiety. Similarly, in the general formula (2), although the allylic group is bonded to each phenol monomer portion in the resin represented by the general formula (2), the resin of the present invention also contains only the phenolic phenol. A portion of the phenolic monomer portion of the body is bonded with an allyl group and a phenolic monomer portion having no unalkened allyl group. The resin represented by the formula (1) of the present invention is preferably a group having an allyl ether group of 50 mol% or more of all the phenol monomer portions in the resin, more preferably 70. If the molar percentage is more than the allyl ether group, particularly preferably 90 mol% or more, the allyl ether group is bonded. Similarly, as the resin represented by the formula (2) of the present invention, it is preferred that 50% by mole or more of all the phenol monomer portions in the resin are bonded with an allyl group, and more preferably 70% by mole or more. The bond has an allyl group, particularly preferably 90 mol% or more with an allyl group bonded. In the resin of the present invention, the ratio of the monomer unit having an allyl ether group or an allyl group in the entire phenol monomer portion can be calculated, for example, from the allyl equivalent. The allylic equivalent of the resin of the present invention is preferably 220 g/eq or more and 600 g/eq or less, more preferably 220 g/eq or more and 300 g/eq or less. The allyl equivalents were determined by the methods described in the following examples. Here, the term "allyl ether group or allyl group" is bonded to a phenol monomer moiety, and an allyl ether group or an allyl group is bonded to a benzene ring of a phenol monomer moiety. Further, the phenol monomer portion means a portion derived from a phenol which is one of the raw materials of the resins among the resins represented by the general formulae (1) and (2).

In the general formulae (1) and (2), when n is 2 or more, a plurality of q may be the same or different.

In the general formulae (1) and (2), the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R may be linear, may be branched, or may be cyclic. Specific examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, a pentyl group, an isopentyl group, and the like. Tripentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, 1-octyl, isooctyl, trioctyl, adamantyl and the like. In addition, examples of the unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R include a linear, branched or cyclic aliphatic hydrocarbon group having at least one double bond or triple bond. Examples of the unsaturated aliphatic hydrocarbon group include a group in which one or more carbon-carbon single bonds in each of the above-described saturated aliphatic hydrocarbon groups are substituted by a double bond or a triple bond. Specifically, Examples thereof include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 2-methylallyl group, a 1,1-dimethylallyl group, and a 3-methyl-2-butenyl group. a linear or branched alkenyl group such as 3-methyl-3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl or nonenyl; ethynyl, propyl-2 -Alkyn-1-yl and other alkyne a cycloalkenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a 4-methylcyclohexenyl group, a 4-ethylcyclohexenyl group or the like; A polymer of acetylene or butadiene, isopropylene or a base of such copolymers. Further, in the case where the unsaturated aliphatic hydrocarbon group is an alkenyl group, both the trans form and the cis form are contained.

Examples of the aryl group represented by R include a phenyl group, a methylphenyl group, an ethylphenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the aryl group is preferably 6 or more and 12 or less. Examples of the aralkyl group represented by R include a benzyl group, a methylbenzyl group, and a phenethyl group. The number of carbon atoms of the aralkyl group is preferably 7 or more and 14 or less. The alkoxy group represented by R is preferably a carbon number of 1 to 10, and examples thereof include those corresponding to the above-mentioned respective saturated aliphatic hydrocarbon groups.

In the general formulae (1) and (2), R which is adjacent to the same ring may be bonded to each other to form a condensed ring. Examples of the condensed ring formed in this case include naphthalene, anthracene, phenanthrene, and the like.

The ICI viscosity of the resin of the present invention at 150 ° C is preferably 5 Pa from the viewpoint of smoothly producing a semiconductor sealing material obtained by kneading with an inorganic filler or the like. Below s, more preferably 3Pa. Below s, especially good for 1Pa. s below. This viscosity can be measured by the method described in the following examples.

In the above formula (1) and formula (2), n represents a value of 0 or more and 20 or less, and preferably a value of more than 0 and 20 or less. The upper limit of n is preferably a value such that the melt viscosity (ICI viscosity) of the phenolic phenol resin of the present invention at 150 ° C is preferably 5 Pa. s below, more preferably 3Pa. s is below, and further preferably 1 Pa. s below. Since the phenolic phenol resin of the present invention is an aggregate of polymers having various molecular weights, the value of n is represented by the average value of the aggregate.

Further, the number average molecular weight Mn of the resin of the present invention is preferably 500 or more and 5,000 or less, more preferably 500 or more and 3,000 or less. The number average molecular weight was measured by a GPC (Gel Permeation Chromatography) measuring apparatus using a calibration curve based on standard polystyrene using the following apparatus and conditions.

GPC measuring device

Model: Waters e2695

Column: LF-804

Measuring condition

Column pressure: 2.7MPa

Dissolution: THF (Tetrahydrofuran, tetrahydrofuran) flow rate 1mL / min

Temperature: 40 ° C

Detector: Spectroscopic Spectrometer (Waters 2489)

Wavelength: 254nm and RI

Injection volume: 50μL

Sample concentration: 5mg/mL

The resin of the present invention can be cured by a reaction with a maleimide compound or the like to provide a cured product which is excellent in heat resistance and excellent in flame retardancy. Further, the cured product obtained by the reaction of the resin of the present invention with a maleimide compound or the like is low in water absorbability. As described above, the resin of the present invention exhibits the following effects which are difficult to obtain by the conventional phenol resin, whereby a maleic imine composition having both heat resistance, flame retardancy, and low water absorbability can be obtained.

The resin of the present invention can be preferably obtained by subjecting a biphenyl aralkyl phenol resin represented by the above formula (I) having an extended biphenyl bridge group to allyl etherification using an allyl halide. Further, the allyl-modified biphenyl aralkyl phenol resin represented by the formula (2) can be subjected to heating by heating the allyl ether-modified biphenyl aralkyl phenol resin of the formula (1). Leysin rearranges the reaction and is preferably obtained. However, the resin of the present invention is not limited to those obtained by the above methods.

Hereinafter, an example of a method for producing an aralkyl phenol resin represented by the formula (I) will be described, but the method is not limited thereto.

[Method for producing aralkyl phenolic resin]

The aralkyl phenol resin represented by the formula (I) can be represented by the following formula (4) (for example, having 4,4'-exophenyl, 2,4'-biphenyl Base, 2, 2'-extended biphenyl, etc. The compound) is preferably produced by a single reaction in the presence of an acid catalyst in the presence of an acid catalyst or in the absence of a catalyst.

(wherein, X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group)

The phenols are not particularly limited, and examples thereof include phenol, cresol, ethylphenol, n-propylphenol, octylphenol, nonylphenol, phenylphenol, xylenol, methylpropylphenol, and dipropylene. Phenol, dibutyl phenol, guaiacol, ethyl guaethol, trimethyl phenol, naphthol, methyl naphthol, bisphenol, bisphenol A, bisphenol F, allyl Phenol or the like may be used alone or in combination of two or more.

The phenol is preferably phenol or cresol, more preferably phenol.

Examples of the compound represented by the formula (4) (biphenyl type crosslinking agent) include 4,4′-bis(halogenated methyl)biphenyl and 2,4′-bis(halogenated methyl)biphenyl. 2,2'-bis(halogenated methyl)biphenyl, 4,4'-bis(alkoxymethyl)biphenyl, 2,4'-bis(alkoxymethyl)biphenyl, 2,2' -bis(alkoxymethyl)biphenyl, 4,4'-bis(hydroxymethyl)biphenyl, 2,4'-bis(hydroxymethyl)biphenyl, 2,2'-di(hydroxymethyl) ) Biphenyl, etc. These may be used alone or in combination of two or more.

Here, examples of the halogen atom represented by X in the general formula (4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and in particular, a chlorine atom is preferred. The alkoxy group having 1 to 6 carbon atoms is not particularly limited, and is preferably a carbon number of 1 to 4, more preferably a methoxy group or an ethoxy group.

Preferred compounds represented by the formula (4) include 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 4,4'- Bis(ethoxymethyl)biphenyl.

When the compound represented by the formula (4) is reacted with a phenol, an acid catalyst is preferably used. As the acid catalyst, organic acids such as oxalic acid, formic acid, acetic acid, and sulfur can be preferably used. Friedel-Crafts type catalysts such as acid, p-toluenesulfonic acid and diethyl sulfate. In the case where a biphenyl type crosslinking agent having a halogenated methyl group is used as the compound represented by the formula (4), the reaction can be appropriately carried out even in the absence of an acid catalyst.

An aralkyl phenolic resin of the formula (I) (also known as a aralkyl group) can be obtained by reacting a compound represented by the formula (4) with a phenol in the presence or absence of an acid catalyst. Bridge phenolic phenolic resin). The phenols can also be reacted in the form of a mixture. After the completion of the reaction, the unreacted phenols may be heated to a reduced pressure or heated while being blown into an inert gas to be distilled off the outside of the system. Further, the acid catalyst can be removed by washing with water or the like.

[Method for producing modified biphenyl aralkyl phenolic resin]

The allyl ether-modified biphenyl aralkyl phenol resin represented by the formula (1) of the present invention can be subjected to allylation of the aralkyl phenol resin represented by the formula (I) by a known method. The reaction is preferably obtained. As such a method, for example, a method of reacting an aralkyl phenol resin represented by the formula (I) with an allyl halide in the presence of a basic catalyst can be mentioned. As an example of the specific procedure, an aralkyl phenol resin represented by the formula (I) which is a raw material is dissolved in an organic solvent or the like to obtain a resin solution, and then a basic catalyst is added to the resin solution, followed by addition of an allyl group. An allyl halide such as chlorine causes the hydroxy group of the aralkyl phenolic resin to be allylated (allyl etherified). The alkaline catalyst and the allyl halide may be simultaneously added to the resin solution, or the allyl halide may be added before the basic catalyst. In this case, the following phenolation reaction is simultaneously or/and continuously performed. And allylation reaction.

Examples of the organic solvent used herein include alcohols such as methanol, n-propanol and n-butanol, ketones such as acetone and methyl ethyl ketone, and N,N-dimethylformamide and dimethyl amide. An aprotic polar solvent such as hydrazine, but is not limited thereto. The amount of the organic solvent used may be an amount that allows the resin to be uniformly dissolved. In the present reaction, it is preferred that substantially no water is used. Specifically, the amount of water used is preferably less than 2% by mass, preferably 1% by mass or less, based on the amount of the aralkyl phenol resin represented by the formula (I) which is a raw material. The amount of water used herein is the amount of water in the reaction system at the start of the reaction of the allylation reaction.

Examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. The amount of the basic catalyst to be added is preferably 1.0 equivalent or more and 2.0 equivalents or less, more preferably 1.0 equivalent or more and 1.5 equivalent or less, based on the hydroxyl group of the aralkyl phenol resin represented by the formula (I). 1.0 equivalent or more and 1.2 equivalent or less. When the amount of the basic catalyst added is 1.0 equivalent or more, the hydroxyl group of the aralkyl phenol resin represented by the formula (I) is sufficiently allyylated, and therefore, if it is 2.0 equivalent or less, the unreacted reaction is suppressed. The residual amount of sodium hydroxide is preferred because it is easy to carry out the removal step.

One of preferred aspects of the aralkyl phenol resin represented by the formula (I) is an aralkyl phenol resin wherein R is a hydrogen atom and has no substituent.

The average value of the degree of condensation n of the aralkyl phenol resin which is a preferred embodiment is preferably 0.5 or more and 20.0 or less, more preferably 2.0 or more and 10.0 or less. Further, the number average molecular weight Mn of the resin of the present invention is preferably 500 or more and 5,000 or less, more preferably 500 or more and 3,000 or less. The number average molecular weight is determined by the above method.

The phenolic hydroxy group in the aralkyl phenolic resin is phenolated by the addition of an alkaline catalyst. The phenolation reaction is preferably carried out at room temperature (25 ° C) or more and at 100 ° C or less for 1 hour or longer and 10 hours or shorter.

As the allyl halide, allyl chloride, allyl bromide, allyl iodide or the like can be used. The amount of the allyl halide to be added is preferably 1.0 equivalent or more and 2.0 equivalent or less, more preferably 1.0 equivalent or more and 1.5 equivalent or less, based on the basic catalyst. When the amount of the allyl halide added is 1.0 equivalent or more, the rate of progress of the allylation reaction can be made to a certain level or more. Therefore, when the amount is more than 2.0 equivalents, the raw material removal step is easy, which is preferable.

The temperature of the allylation reaction is not particularly limited, but is preferably carried out at room temperature (25 ° C) or more and 100 ° C or lower. By setting it as a room temperature or more, the reaction can be carried out at a constant speed or higher, and by setting it to 100 ° C or less, it is preferable to prevent the side reaction from being complicated and to easily obtain the desired allylated resin. From this point of view, the temperature of the more preferred allylation reaction is 50 or more and 90 ° C or less. About the time of the allylation reaction, for example, at the above room temperature When the reaction is carried out at (25 ° C) or higher and at 100 ° C or lower, it is preferably 1 hour or longer and 10 hours or shorter.

By the above steps, the allyl ether-modified biphenyl phenol resin represented by the formula (1) can be easily obtained.

Further, by subjecting the obtained allyl ether-modified biphenyl phenol resin represented by the general formula (1) to a Claisen rearrangement reaction, the allyl ether group can be rearranged on the phenol nucleus. Further, an allyl modified biphenyl phenol resin represented by the formula (2) is obtained. The temperature of the rearrangement reaction is preferably from 150 ° C to 250 ° C, more preferably from 180 ° C to 230 ° C, still more preferably from 180 ° C to 200 ° C. By setting the reaction temperature to 150 ° C or higher, the progress of the Claisen rearrangement reaction can be accelerated, and by setting the reaction temperature to 250 ° C or lower, the decomposition of the raw material or the target can be more reliably prevented, and the target can be easily obtained. The allyl modified biphenyl phenol resin is preferred. The Claisen rearrangement reaction is preferably carried out under an inert gas atmosphere such as nitrogen.

The resin represented by the above formula (1) of the present invention and/or the resin represented by the formula (2) of the present invention can be used as a curing composition containing a maleic imine compound as follows. Further, the resin represented by the general formula (2) of the present invention can be used as a hardener for an epoxy resin.

Next, the composition of the present invention will be described. The composition of the present invention contains the resin represented by the formula (1) of the present invention and/or the resin represented by the formula (2) of the present invention and a compound having two or more maleimine groups in one molecule. (hereinafter also referred to as "maleimide compound").

Examples of the maleinimide compound include those represented by the following formula (5) or formula (6).

(wherein Y is a divalent group having one carbon-carbon double bond as a main chain, and Z is a divalent group having 2 to 40 carbon atoms)

(wherein Y is a divalent group having one carbon-carbon double bond as a main chain, and s is a value of 0 or more)

In the above formulae (5) and (6), Y is preferably -CR ¹ =CR ² - (wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 or more and 5 or less carbon atoms). Further, Z may be a cyclic, linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, or a combination of two or more of them.

The s is preferably 0 or more and 4 or less, more preferably 0 or more and 2 or less.

As a specific maleic imine compound, it may be an aliphatic (non-cyclic) structure such as 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,6-Bismaleimide-(2,4,4-trimethyl)hexane, N,N'-decamethylenebismaleimide, N,N'-octamethylene Bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-trimethylene bismaleimide, N, N'-extended ethyl bismale The imine may also be an aliphatic cyclic structure or an aromatic cyclic structure of the skeleton of the compound, such as: bis[(2,5-di- oxy-2,5-dihydropyrrole-1-yl)- Bicyclo[2,2,1]heptane, N,N'-p-phenylene bismaleimide, N,N'-interphenylene bismaleimide, N,N' -2,4-tolyl bismaleimide, N,N'-2,6-tolyl bismaleimide, N,N'-4,4-diphenylmethane Bismale Amine, N, N'-3,3-diphenylmethane bismaleimide, N,N'-4,4-diphenyl ether, bismaleimide, N,N'-3,3- Diphenyl ether bismaleimide, N,N'-4,4-diphenyl sulfide dimaleimide, N,N'-3,3-diphenyl sulfide Bismaleimide, N,N'-4,4-diphenyl bis-maleimide, N,N'-3,3-diphenyl bis-maleimide, N,N'- 4,4-diphenyl ketone bismaleimide, N,N'-3,3-diphenyl ketone bismaleimide, N,N'-4,4-biphenyl bismale Yttrium, N,N'-3,3-biphenylbismaleimide, N,N'-4,4-diphenyl-1,1-propane, bismaleimide, N, N'-3,3-diphenyl-1,1-propane bismaleimide, 3,3'-dimethyl-N,N'-4,4-diphenylmethane Bismale Amine, 3,3'-dimethyl-N,N'-4,4'-biphenylbismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, Bis[4-(3-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2 - bis[4-(3-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2, 2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1, 1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-maleimidophenoxy)biphenyl, bis[4-(3-maleimide phenoxy) Phenyl] ketone, bis[4-(3-maleimidophenoxy)phenyl]-anthracene, [4- (3-acyl imine maleate) phenyl] sulfone, bis [4- (3-acyl imine maleate) phenyl] ether. These bismaleimide compounds may be used alone or in combination of two or more.

The content of the maleic imine compound in the composition of the present invention is the allyl ether-modified biphenyl aralkyl phenol resin represented by the general formula (1) of the present invention and/or represented by the formula (2) Ratio of the allyl equivalent number of the allyl modified biphenyl aralkyl phenolic resin to the maleimide equivalent of the maleimide compound [maleimide equivalent number / ally The number of base equivalents is preferably in the range of 0.80 to 2.00, more preferably 0.80 to 1.60.

When the ratio is 0.80 or more, the heat resistance (glass transition temperature) or expandability (linear expansion ratio) of the cured product tends to be sufficient and preferable. Further, by the ratio of 2.00 or less, it is difficult to produce the problem of the previously known bismaleimide compound, that is, the fluidity is deteriorated, the operation is difficult, the hardening is not easy to be performed at a low temperature, and the toughness of the obtained hardened material is hardly obtained. It is preferable to wait for a bad situation such as being brittle and becoming brittle.

Further, when the number of functional groups such as the number of equivalents of maleimine or the number of allyl groups is set to A (g/eq), and the amount of addition is B (g), By B/A ([B x C/100] / A when the purity of the compound is C%). In other words, the functional group equivalent such as maleimine equivalent or allylic equivalent indicates the molecular weight of the compound corresponding to each functional group, and the number of equivalent functional groups indicates the functional amount per unit mass (addition amount) of the compound. The number of bases (the number of equivalents).

The composition of the present invention may contain a hardening accelerator. The curing accelerator may be any one that promotes the curing of the composition containing the maleimide compound and the allyl-containing resin, and generally includes a user as a radical initiator. Examples of such a curing accelerator include mercapto peroxide, hydrogen peroxide, ketone peroxide, a peroxide having a third butyl group, an organic peroxide such as a peroxide having a cumene group, and the like. . For example, benzammonium peroxide, p-chlorobenzothymidine peroxide, 2,4-dichlorobenzidine peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, ruthenium peroxide (capryl) Peroxide), ruthenium peroxide, acetonitrile peroxide, bis(1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, tert-butyl hydroperoxide, hydroperoxide, methane, cumene hydroperoxide , di-tert-butyl peroxide, dicumyl peroxide (also in the case of DCPO), 2,5-dimethyl-2,5-di(t-butylperoxy)hexane 2,5-di(perbenzoic acid) 2,5-dimethylhexyl ester, tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl peroctoate, isobutyric acid peroxide An organic peroxide such as a tributyl acrylate or a di-tert-butyl phthalate may be used alone or in combination of two or more. When the curing accelerator is used, the amount thereof to be added to the composition of the present invention is preferably 0.01 parts by mass or more and 8 parts by mass or less, more preferably 1 part by mass or more, based on 100 parts by mass of the resin of the present invention. 6 parts by mass or less.

Further, the composition of the present invention may contain other optional ingredients. As such an optional component, depending on the use of the composition of the present invention, for example, an additive such as a filler, an imidazole compound for curing promotion, a coupling agent, a pigment, or a dye can be preferably used. Further, a solvent such as an organic solvent can also be used.

As the filler, any of an organic filler or an inorganic filler can be used. As As the inorganic filler, for example, amorphous cerium oxide, crystalline cerium oxide, aluminum oxide, calcium citrate, calcium carbonate, talc, mica, barium sulfate or the like can be used. It is especially preferred to use amorphous cerium oxide and crystalline cerium oxide. The particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more and 150 μm or less in consideration of the filling ratio. The blending ratio of the inorganic filler is not particularly limited, but the ratio of the inorganic filler to the maleidanilide composition is preferably 70% by mass or more and 95% by mass or less, and more preferably 70% by mass or more. And 90% by mass or less. By setting the blending ratio of the inorganic filler within this range, it is difficult to increase the water absorption rate of the cured product of the composition, which is preferable.

The amount of the resin of the present invention in the composition of the present invention varies depending on the use of the composition of the present invention. When, for example, the composition of the present invention does not contain a filler, it is preferably in the composition of the present invention. 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 60% by mass or less. Further, when the composition of the present invention contains a filler, for example, the amount of the resin of the present invention is preferably 5% by mass or more and 25% by mass or less, more preferably 5% by mass or more in the composition of the present invention. And 20% by mass or less.

In the composition of the present invention, the total amount of the components other than the resin, the maleimide compound, the hardening accelerator and the filler of the present invention varies depending on the use of the composition of the present invention, and is generally preferred. The resin is 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less based on the resin of the present invention.

In order to prepare the composition of the present invention, for example, a resin such as the resin of the present invention, a maleimide compound, and optionally a hardening accelerator, an inorganic filler, and other additives may be uniformly mixed using a stirrer or the like, and heating may be used. The kneading machine such as a roll, a kneader or an extruder is kneaded in a molten state, and the kneaded material is cooled and pulverized as needed.

The composition of the present invention can preferably obtain a cured product by a conventional heat treatment. For example, the heat treatment is affected by the presence or absence of a radical initiator or a hardening accelerator, but it is preferably pressurized at a temperature of preferably 150 to 280 ° C, more preferably 150 to 250 ° C under normal pressure or using an autoclave or the like. The lowering is preferably 1 to 24 hours, more preferably 1 to 12 hours.

The resin of the present invention represented by the above formula (1) or (2) and the maleidanilide composition using the same are not particularly limited, and the heat resistance, flame retardancy, and low water absorbability of the cured product are sufficiently exhibited. It can be preferably used as a sealing material for sealing a semiconductor element. For example, after the lead frame or the like on which the semiconductor element is mounted is placed in a metal cavity, the maleimide composition is molded by a molding method such as transfer molding, compression molding, or injection molding, and 120 to 300 ° C is used. The composition is cured by heat treatment at a temperature of left and right, whereby a semiconductor device can be preferably obtained.

Further, the composition of the present invention can be uniformly dissolved in a known solvent such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethylformamide to produce a varnish solution. The varnish solution is applied or impregnated into a porous glass substrate such as glass, glass fiber, paper, aromatic polyamide fiber, or the like, followed by heat treatment (semi-hardening) to produce a prepreg for a printed substrate. Further, by using a plurality of prepreg layer layers for the obtained printed substrate, heat treatment is performed while pressing as needed, and the laminate of the matrix resin formed by using the composition of the present invention can be preferably produced.

Further, a metal clad laminate can be obtained by laminating a metal foil on one side or both sides of a laminate or a prepreg, and performing heat treatment while pressing. The metal clad laminate is formed into a circuit pattern by an etching process, and can be preferably used as a printed wiring board.

The resin of the present invention represented by the above formula (1) or (2) and the maleidanilide composition using the same sufficiently exhibit heat resistance, flame retardancy, and low water absorbability of the cured product, and sealing of the semiconductor element It can be used as a material for construction, an adhesive, a paint, etc., in addition to the use of electrical and electronic parts such as materials or printed wiring board materials. In particular, the resin of the present invention and the composition of the present invention sufficiently exhibit the characteristics of excellent flame retardancy and heat resistance, and can be preferably used for parts which are used at a high temperature or in an easily combustible state, for example, for vehicle use. Electronic parts related to semiconductors, electronic parts used in high voltage display devices, large batteries, etc.

Furthermore, it is needless to say that the present invention provides a maleic imide tree containing the resin of the present invention represented by the above formula (1) or (2) in addition to the resin and composition of the present invention. Hardener for fat. The curing agent may be one containing only the resin of the present invention, or may contain various additives in addition to the resin of the present invention. Examples of the additive include various components listed in the above-mentioned contents as components other than the maleimide compound used in the composition of the present invention. Further, the present invention also provides a method of hardening a maleic imide compound using the resin of the present invention.

Example

The invention will now be described more specifically by way of examples. However, the scope of the invention is not limited to the embodiments. Unless otherwise stated, "parts" means "parts by mass". Also, "%" means "% by mass".

The evaluation methods used in the examples are shown below.

(1) Allyl equivalent (eq/g): Measured by an iodine titration method based on JIS K0070.

(2) Hydroxyl equivalent (eq/g): Measured by hydroxyl equivalent measurement based on JIS K0070.

(3) ICI viscosity (Pa.s): The MODEL CV-1S manufactured by TOA Industrial Co., Ltd. was used as an ICI cone and plate viscometer. The plate temperature of the ICI viscometer was set at 150 ° C, and a specific amount of the sample was weighed. The weighed resin was placed on the plate portion, pressed from the upper portion with a cone, and left for 90 sec. Rotate the cone and read its torque value as the ICI viscosity.

(4) Infrared absorption spectroscopy (IR) analysis

The IR analysis of the resin was carried out using a Fourier transform infrared spectroscopy FT-IR analyzer manufactured by PerkinElmer.

(5) Glass transition temperature (Tg, °C): Measurement was carried out under the conditions of a temperature increase rate of 5 ° C/min using a thermomechanical analyzer (manufactured by Hitachi, Ltd., TMA-7100). The test piece size was set to 10 mm × 10 mm × 4 mm.

(6) 5% mass reduction temperature (Td5), heating mass reduction rate, and residual carbon ratio: TG/DTA (manufactured by Hitachi High-Tech Science Co., Ltd., TG/DTA7200), the 5% mass reduction temperature (Td5) and the mass reduction rate at 550 ° C were measured under the conditions of a temperature increase rate of 10 ° C / min. The amount of the sample was set to 20 mg.

(7) Flame retardancy: Evaluation was based on UL-94. The total burning time of the five test pieces was totaled and set as the burning time.

[1] Preparation of allyl ether modified biphenyl aralkyl phenolic resin

<Example 1>

As a raw material resin, p, q and r used in the above formula (I) are 0, and the ICI viscosity (150 ° C) is 0.42 Pa. s, a biphenyl aralkyl phenol resin (hereinafter referred to as a raw material resin a) having a hydroxyl equivalent of 217 (g/eq). Into a four-necked flask equipped with a thermometer, a cooler, and a stirring device, 143.5 g (hydroxyl 0.66 mol), 143.5 g of 1-propanol, and sodium hydroxide 29.40 g (0.74 mol) as a basic catalyst were charged into a four-necked flask equipped with a thermometer, a cooler, and a stirring device. The phenolation reaction of the aralkyl phenol resin was carried out by reacting at 50 ° C for 5 hours. The allyl etherification reaction was carried out by adding 58.91 g (0.77 mol) of allyl chloride to the reaction mixture and reacting at 70 ° C for 4 hours. The reaction mixture obtained was heated to 130 ° C, and unreacted allyl chloride and a solvent were removed under reduced pressure. After cooling to 95 ° C, it was washed 10 times with pure water to remove the by-product salt. After washing, the temperature was raised to 150 ° C, and water was removed under reduced pressure, whereby Resin A as a product was obtained. The ICI viscosity of Resin A was measured. Further, the allylic equivalent of the resin A was measured. These results are shown in Table 1 below. The OH equivalent of the raw material resin a and the ICI viscosity are also shown in the table. Further, IR analysis of the raw material resin a and the resin A was carried out by the above method. The IR analysis chart of the obtained raw material resin a is shown in Fig. 1, and the IR analysis chart of the resin A is shown in Fig. 2.

As is clear from Fig. 2, in the diagram of Resin A, the absorption of allyl ether was observed in the vicinity of 1200 cm ^-1 . Further, the absorption of the carbon-carbon double bond derived from the allyl group was observed in the vicinity of 900 cm ^-1 . On the other hand, the absorption of the phenolic hydroxyl group in the vicinity of 3400 cm ^-1 which can be seen in the diagram of the raw material resin a (Fig. 1) is hardly observed in the resin A.

From the above results, it was confirmed that the obtained resin A is an allyl ether-modified biphenyl aralkyl phenol resin represented by the formula (1) obtained by etherifying a phenolic hydroxyallyl group of the raw material resin a. Further, it was confirmed from allyl equivalents that among all the phenol monomer portions, almost all (90 mol% or more) of the phenol monomers had an allyl ether group bonded thereto.

[2] Preparation of allyl modified biphenyl aralkyl phenolic resin

<Example 2>

The allyletherated biphenyl aralkyl resin A obtained in Example 1 was added to a four-necked flask equipped with a thermometer, a cooler, and a stirring apparatus, and the Claisen rearrangement reaction was carried out at 190 ° C for 8 hours under a nitrogen atmosphere. Thereby, the resin B as a product was obtained. The ICI viscosity of the resin B was measured. Further, the allylic equivalent of the resin B was measured. These results are shown in Table 1 below. Further, IR analysis of the resin B was carried out by the above method. The obtained IR analysis chart is shown in Fig. 3.

Further, as is clear from Fig. 3, compared with the IR pattern of the resin A represented by the formula (1) shown in Fig. 2, the IR pattern of the resin B shown in Fig. 3 was observed in the vicinity of 1200 cm ^-1 . The absorption of the allyl ether disappeared, and the increase in the absorption of the phenolic hydroxyl group observed in the vicinity of 3400 cm ^-1 was remarkable. Therefore, it was confirmed that the resin A as the allyl ether-modified biphenyl aralkyl phenol resin represented by the formula (1) is converted to the allyl group represented by the formula (2) by the Claisen rearrangement reaction. The modified biphenyl aralkyl phenol resin, that is, the obtained resin B is a resin represented by the formula (2). Further, it was confirmed from allyl equivalents that among all the phenol monomer portions, almost all (90 mol% or more) of the phenol monomers were bonded with an allyl group.

The maleidinoimine composition was prepared using the modified biphenyl aralkyl phenol resin obtained in Examples 1 and 2, and the cured product was measured for the cured product obtained from the maleimide composition. These results are summarized in Table 2.

[3] Preparation and evaluation of maleic imine composition or epoxy resin composition and hardened material I

<Example 3>

The allyl etherified biphenyl aralkyl phenol resin A obtained in Example 1 was used as a phenol resin, BMI-1000 Bismaleimide (N, N'-4, manufactured by Daiwa Kasei Kogyo Co., Ltd., 4-diphenylmethane bismaleimide) (maleimide equivalent: 179 g/eq, purity: 93%) as a maleic imine compound, dicumyl peroxide (DCPO) as a hardening promotion A maleimide composition was prepared by using a chelating agent (MSR-2212) manufactured by Ronson Corporation as a filler. Specifically, the respective components were mixed according to the composition shown in the following Table 2, and the mixture was pulverized by two rolls at a temperature of 80 ° C to prepare a powder of the maleic imide composition.

A test piece was prepared from a 40 Φ tablet prepared by using the obtained maleic imide composition powder by a transfer molding machine, and subjected to post-hardening treatment at 180 ° C for 8 hours under normal pressure. After the obtained cured product was cut into a specific size or weight, the glass transition temperature, the 5% mass reduction temperature (Td5), and the heating mass reduction rate were measured by the above methods, and the flame retardancy was evaluated.

<Example 4>

The allylic biphenyl aralkyl resin B obtained in Example 2 was used as the phenol resin, and the maleimide composition was prepared according to the composition of the following Table 2, and the same procedure as in Example 3 was carried out. The cured product was obtained, and the 5% mass reduction temperature (Td5) and the heating mass reduction rate were measured, and the flame retardancy was evaluated.

<Comparative Example 1>

It is represented by the following general formula (7) and is liquid at room temperature (25 ° C) (E-type viscosity (25 ° C): 1770 mPa·s), a hydroxyl equivalent of 144 g/eq, and an allyl equivalent of 144 g/eq. An allyl phenol-based phenol resin (hereinafter also referred to as Resin X) was used as a phenol resin, and a cured product was obtained in the same manner as in Example 3 except that the maleic imine composition was prepared according to the composition of Table 2 below. The 5% mass reduction temperature (Td5) and the heating mass reduction rate were measured, and the flame retardancy was evaluated.

<Comparative Example 2>

A triphenylmethane type phenol resin (ICI viscosity (150 ° C): 0.9 Pa.s) (hereinafter also referred to as resin Y) represented by the following general formula (8) is used as a phenol resin or a triphenylmethane type epoxy resin. Resin EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin, triphenylphosphine (also in the case of TPP), as a hardening accelerator, and cerium oxide (MSR-2212) manufactured by Ronson Corporation As a filler, a high heat resistance EMC (Epoxy Molding Compound) composition was prepared. Specifically, the components were mixed according to the composition shown in Table 2, and pulverized by two rolls at a temperature of 80 ° C to prepare an EMC powder.

A test piece was prepared from a 40 Φ tablet prepared using the obtained EMC powder by a transfer molding machine, and subjected to post-hardening treatment at 180 ° C for 8 hours under normal pressure. After the obtained cured product was cut into a specific size or weight, the glass transition temperature, the 5% mass reduction temperature (Td5), and the heating mass reduction rate were measured by the above methods, and the flame retardancy was evaluated.

As shown in Table 2, it was found that the maleine compositions of Examples 3 and 4 using the modified biphenyl aralkyl phenol resins A and B of the present invention have high heat resistance and remarkable flame retardancy. On the other hand, it is understood that the maleidinoimine composition of Comparative Example 1 using the allyl-modified phenol resin which is different from the resin of the present invention, and the resin Y which is a phenol resin different from the resin of the present invention. The epoxy resin composition of Comparative Example 2 was extremely inferior to Examples 3 and 4 in terms of flame retardancy. Further, it is understood that the compositions of Comparative Examples 1 and 2, particularly the composition of Comparative Example 2, are also inferior to Examples 3 and 4 in terms of heat resistance.

[4] Preparation and evaluation of maleic imine composition or epoxy resin composition and hardened material II

The evaluation of the cured product in the following evaluation II was carried out by the methods described in the following (i) to (iii).

(i) Glass transition temperature (Tg, °C): It was measured at a temperature increase rate of 5 ° C/min using a thermomechanical analyzer (manufactured by Hitachi, Ltd., TMA-7100). Further, the temperature was raised to 230 ° C before the measurement to remove the strain of the test piece. The size of the test piece was set to 5 mm × 5 mm × 2 mm.

(ii) 5% mass reduction temperature (Td5) and 550 °C residual carbon ratio: TG/DTA (manufactured by Hitachi High-Tech Science Co., Ltd., TG/DTA7200) in a nitrogen atmosphere (N ₂ flow rate: 50 ml/min) The 5% mass reduction temperature (Td5) and the residual carbon ratio at 550 ° C were measured under the conditions of a heating rate of 10 ° C / min. The residual carbon ratio was determined as a value obtained by subtracting the mass reduction rate (%) at 550 ° C from 100%. The amount of the sample was set to 5 mg.

(iii) Water absorption rate (%): The test piece was immersed in pure water at 95 ° C, and the mass increase rate calculated from the mass before immersion and the mass after immersion for 24 hours was taken as the water absorption rate. The water absorption rate is an index indicating moisture resistance, and the smaller value indicates that the moisture resistance is good. The test piece size was set to 15 mm × 30 mm × 2 mm.

<Example 5>

The allyl etherified biphenyl aralkyl phenol resin A obtained in Example 1 was used as a phenol resin, BMI-1000 of BMI-1000 of Dahe Chemical Industry Co., Ltd. (N, N'-4, 4 -diphenylmethane bismaleimide) (maleimide equivalent: 179 g/eq, purity: 93%) as a maleic imine compound and dicumyl peroxide (DCPO) as a hardening promotion A maleic imide composition (maleimide composition containing no inorganic filler such as cerium oxide) is prepared. Specifically, the components were mixed according to the compositions shown in Table 3 below. The method of mixing is to heat the allyl etherified biphenyl aralkyl phenol resin A to 160 ° C and stir, and add N, N'-4,4-diphenylmethane bismaleimide while stirring. Melt mixing. After the N,N'-4,4-diphenylmethane bismaleimide is completely melted, it is cooled to 130 ° C, and then dicumyl peroxide is added and stirred to prepare a maleimide composition. .

The obtained maleic imine composition was vacuum-defoamed, cast into a mold heated to 170 ° C, heat-treated at 200 ° C for 90 minutes, and then heat-treated at 230 ° C for 90 minutes, thereby obtaining a thickness of 2 mm × A cured product having a width of 60 mm and a length of 150 mm. After the obtained cured product was cut into a specific size or weight, the glass transition temperature, the 5% mass reduction temperature (Td5), and the residual carbon ratio at 550 ° C were measured by the above methods to evaluate the water absorption.

<Example 6>

Using the allylated biphenyl aralkyl resin B obtained in Example 2 as a phenol tree A cured product was obtained in the same manner as in Example 5 except that the maleimide composition was prepared according to the composition of the following Table 3, and the glass transition temperature, the 5% mass reduction temperature (Td5), and the 550 ° C residue were measured. Carbon rate, evaluation of water absorption.

<Comparative Example 3>

An allyl ether phenolic phenol resin (hereinafter also referred to as resin α) represented by the following general formula (α) and having an allyl equivalent of 206 g/eq was used as a phenol resin, and a horse was prepared according to the composition of Table 3 below. A cured product was obtained in the same manner as in Example 5 except that the bismuth imine composition was measured, and the glass transition temperature, the 5% mass reduction temperature (Td5), and the residual carbon ratio at 550 ° C were measured, and the water absorption ratio was evaluated.

<Comparative Example 4>

An allylphenol-based phenol resin (hereinafter also referred to as resin β) represented by the following general formula (β) and having an allyl equivalent of 210 g/eq was used as a phenol resin, and a horse was prepared according to the composition of Table 3 below. A cured product was obtained in the same manner as in Example 5 except that the bismuth imine composition was measured, and the glass transition temperature, the 5% mass reduction temperature (Td5), and the residual carbon ratio at 550 ° C were measured, and the water absorption ratio was evaluated.

<Comparative Example 5>

Using the above resin X as a phenol resin, Malay was prepared according to the composition of Table 3 below. A cured product was obtained in the same manner as in Example 5 except for the imine composition, and the glass transition temperature, the 5% mass reduction temperature (Td5), and the residual carbon ratio at 550 ° C were measured, and the water absorption ratio was evaluated.

<Comparative Example 6>

The above resin Y is used as a phenol resin, a triphenylmethane type epoxy resin EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and 2-ethyl-4-methylimidazole 2E4MZ (Four Nations Chemical Industry) As a hardening accelerator, a high heat resistant epoxy resin composition is prepared. Specifically, each of the components was melt-mixed in accordance with the composition shown in Table 3 below to prepare a highly heat-resistant epoxy resin composition.

The molten mixture of the high heat resistant epoxy resin composition was vacuum defoamed, cast to a mold heated to 170 ° C, heat treated at 200 ° C for 90 minutes, and then heat treated at 230 ° C for 90 minutes, thereby obtaining a thickness of 2 mm. × Hardened material having an amplitude of 60 mm × a length of 150 mm. With respect to the obtained cured product, the glass transition temperature, the 5% mass reduction temperature (Td5), and the residual carbon ratio at 550 ° C were measured by the above method, and the water absorption rate was evaluated.

As shown in Table 3, it is understood that the maleidanilide compositions of Examples 5 and 6 using the modified biphenyl aralkyl phenolic resin A or B of the present invention are pure resins (neat) without a filler. In the case of the resin, it also has high heat resistance as in the case of containing a filler. On the other hand, it is understood that the use of the allyl modified phenol resin or allyl ether different from the resin of the present invention is used. The epoxy resin composition of Comparative Example 3 to 5 of Comparative Example 3 to 5 and the epoxy resin composition of Comparative Example 6 using a phenol resin different from the resin of the present invention were in the range of Examples 5 and 6 in terms of heat resistance. In particular, Comparative Examples 5 and 6 were extremely poor.

Further, it was found that the maleidanilide compositions of Examples 5 and 6 using the modified biphenyl aralkyl phenol resin of the present invention were superior in water absorption to the compositions of Comparative Examples 3 to 6.

Claims (11)

An allyl ether-modified biphenyl aralkyl phenol resin represented by the following formula (1), (wherein R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different, and p, q and r are each independently An integer of 0 to 3 is represented, and n represents a value of 0 to 20, wherein a part of the allylic groups of the plurality of allyl groups in the formula (1) may be substituted with a hydrogen atom). An allyl modified biphenyl aralkyl phenol resin represented by the following formula (2), (wherein R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different, and p, q and r are each independently An integer of 0 to 3 is represented, and n represents a value of 0 to 20, wherein a part of the allylic groups of the plurality of allyl groups in the formula (2) may be substituted with a hydrogen atom). A process for producing an allyl ether-modified biphenyl aralkyl phenol resin according to claim 1, which comprises an aralkyl phenol resin represented by the following formula (I) in the presence of a basic catalyst and an olefin Propyl halide reaction, (wherein R, p, q, r and n are the same as in the formula (1)). A process for producing an allyl-modified biphenyl aralkyl phenol resin according to claim 2, which is an allyl ether-modified biphenyl aralkyl phenol resin obtained by the method of claim 3 Perform a Claisen rearrangement reaction. A composition comprising the allyl ether modified biphenyl aralkyl phenol resin as claimed in claim 1 and/or the allyl modified biphenyl aralkyl phenol resin as claimed in claim 2, having one molecule Two or more compounds of maleimine. The composition of claim 5, which comprises a hardening accelerator. The composition of claim 5, which comprises a filler. A hardened material comprising the composition of claim 5. A sealing material for a semiconductor element comprising the composition of claim 5. A semiconductor device sealed using a sealing material as claimed in claim 9. A laminate comprising the composition of claim 5 as a matrix resin.