JP6755643B2 - Allyl ether-modified biphenyl aralkyl novolac resin, allyl-modified biphenyl aralkyl novolac resin, a method for producing the same, and a composition using the same. - Google Patents

Description

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

As for the cross-linked phenol resin (also referred to as novolak resin) obtained by cross-linking phenols with phenols as a raw material monomer, particularly phenols with alkylene or aralkylene, an epoxy resin composition using the same has generally good workability. Since the cured product is excellent in electrical properties, heat resistance, moisture resistance, adhesiveness, etc., it is widely used in the fields of electrical / electronic parts, structural materials, adhesives, paints, and the like.

In recent years, in applications such as electrical and electronic parts, further improvement is required for various properties of such epoxy resin compositions. For example, when used in electronic components related to in-vehicle semiconductors, electronic components used in display devices using high voltage, large batteries, etc., which are used in harsher environments, high glass transition temperature and high flame retardancy There is a demand for an epoxy resin composition that can provide a cured product that also has the above. On the other hand, from the viewpoint of reducing the environmental load, it is desired that high flame retardancy is exhibited while being halogen-free. However, the epoxy resin composition composed of a phenol resin and an epoxy resin has a limit in the heat resistance that can be obtained due to its structure, and does not meet the requirements.

As a composition exhibiting heat resistance superior to that of an epoxy resin composition, a composition using an allyl-modified phenol compound and a maleimide compound is known. For example, Patent Document 1 describes that a composition having excellent heat resistance can be obtained by blending diallyl bisphenol A and bismaleimide. Further, Patent Document 2 describes that a composition having excellent heat resistance can be obtained by blending an allyl ether resin obtained by allyl etherifying a phenol resin having a cyclohexanenorbornane bond with bismaleimide.

Japanese Unexamined Patent Publication No. 53-134099 Japanese Unexamined Patent Publication No. 8-59533

However, Patent Documents 1 and 2 have not made any study on flame retardancy, and have not proposed a phenol resin that can obtain a maleimide composition having high flame retardancy as well as heat resistance.

Therefore, an object of the present invention is to provide a phenol resin that is halogen-free and can provide a cured product having both a high glass transition temperature and high flame retardancy by reacting with a maleimide compound or the like. Another object of the present invention is to provide a method for producing the above-mentioned phenol resin, a maleimide compound-containing composition using the above-mentioned phenol resin (hereinafter, also simply referred to as a maleimide composition), and a cured product of the resin composition.

As a result of diligent studies to solve the above problems, the present inventors have obtained an allyl ether-modified biphenyl aralkyl novolak resin and / or an allyl-modified biphenyl aralkyl novolac resin obtained by allylating a specific aralkyl novolak resin. The present invention has been completed by finding that a maleimide composition and a cured product having high heat resistance exceeding the heat resistance of a conventional epoxy resin cured product and also having flame retardancy can be obtained.

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

(During the ceremony
A indicates an allyl group and
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 from each other.
j, k, and l each independently represent an integer of 1 to 2.
However, at least one of j, k and l is 2.
p, q and r independently represent integers 0 to 3, respectively.
k + q ≦ 4
n represents a value from 0 to 20.
However, some of the allyl groups represented by A may be substituted with hydrogen atoms. )

The present invention also relates to an allyl-modified biphenyl aralkyl novolac resin represented by the following general formula (2).

(During the ceremony
A indicates an allyl group and
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 from each other.
j, k, and l each independently represent an integer of 1 to 2.
However, at least one of j, k and l is 2.
p, q and r independently represent integers 0 to 3, respectively.
s, t and u each independently represent an integer of 1 to 2.
j + p + s ≦ 5, k + q + t ≦ 4, and l + r + u ≦ 5.
n represents a value from 0 to 20.
However, some of the allyl groups represented by A may be substituted with hydrogen atoms. )

Further, in the present invention, the allyl ether-modified biphenyl aralkyl novolac resin represented by the above general formula (1) in which the aralkyl novolac resin represented by the following general formula (I) is reacted with allyl halide in the presence of a basic catalyst. It provides a manufacturing method of.

(In the formula, R, j, k, l, p, q and r and n are the same as the general formula (1).)

The present invention also provides a method for producing an allyl-modified biphenyl aralkyl novolak resin represented by the general formula (2), which comprises reacting the allyl ether-modified biphenyl aralkyl novolac resin represented by the general formula (1) with a Claisen rearrangement reaction. It is something to do.

The present invention also provides a composition containing the allyl ether-modified biphenyl aralkyl novolac resin and / or the allyl-modified biphenyl aralkyl novolac resin and a compound having two or more maleimide groups in one molecule, and a cured product thereof. Is. The present invention also provides a sealing material for a semiconductor element containing the resin or the composition, a semiconductor device, and a printed wiring board material.

INDUSTRIAL APPLICABILITY The present invention provides a phenol resin that is halogen-free and can provide a cured product having both a high glass transition temperature and high flame retardancy by reacting with a maleimide compound or the like. Further, a method for producing the phenol resin, a maleimide composition containing the phenol resin, a semiconductor encapsulant composed of the maleimide resin composition, a cured product of the maleimide composition, and a semiconductor device containing the cured product are also provided. .. According to the phenol resin of the present invention, it is possible to provide a cured product having very good heat resistance and flame retardancy, and the conventional epoxy resin, the epoxy resin composition composed of the phenol resin and the cured product cannot be used. Since it can be suitably used even in extremely harsh environments, it is suitable for electronic parts related to automotive semiconductors, electronic parts used for display devices using high voltage, large batteries, etc., and has industrial utility potential. Is high.

FIG. 1 is an IR spectrum of the resin represented by the general formula (I) used in the examples. FIG. 2 is an IR spectrum of the resin of Example 1 represented by the general formula (1). FIG. 3 is an IR spectrum of the resin of Example 2 represented by the general formula (2).

Hereinafter, the present invention will be described based on the preferred embodiment thereof.
The present invention relates to an allyl ether-modified biphenyl aralkyl novolac resin represented by the general formula (1) (hereinafter, also referred to as a resin of the general formula (1)) and an allyl-modified biphenyl aralkyl novolac represented by the general formula (2). It relates to a resin (hereinafter, also referred to as a resin of the general formula (2)). 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 novolac resin obtained by cross-linking phenols with biphenylylenes. The substitution position of the allyl group may be added as an allyl ether group to the phenolic hydroxyl group in the above-mentioned biphenyl aralkyl resin by an ether bond, or may be added to the benzene ring of the phenol monomer portion of the biphenyl aralkyl resin.

Of the plurality of allyl groups represented by A in the general formula (1) and the general formula (2), some allyl groups may be substituted with hydrogen atoms. Therefore, among the plurality of A existing in the general formula (1) of the present invention, any one or more A may be a hydrogen atom H. Of the (j + n × k + l) A presents in the general formula (1), the ratio of hydrogen atoms that are unsubstituted, that is, allyl groups is preferably 50% or more, and 70% or more. It is more preferable, and 90 mol% or more is particularly preferable. The ratio of allyl groups to A in the resin of the general formula (1) can be determined by measuring the allyl group equivalent of the resin.

Similarly, of the plurality of A in the general formula (2) of the present invention, any one or more A may be a hydrogen atom H. In the general formula (2), the number of A as an allyl group is preferably 50 mol% or more, preferably 70 mol% or more, based on the number of phenolic hydroxyl groups (OH groups) contained in the formula (2). Is more preferable, and 90 mol% or more is particularly preferable. The ratio of the allyl group to the phenolic hydroxyl group (OH group) in the resin of the general formula (2) can be determined by measuring the allyl group equivalent of the resin.

In any of the resins of the general formulas (1) and (2), the allyl group equivalent is preferably 100 g / eq or more and 400 g / eq or less, more preferably 100 g / eq or more and 350 g / eq or less, and particularly preferably. Is 100 g / eq or more and 300 g / eq or less. The allyl group equivalent is measured by the method described in Examples described later.

In the general formulas (1) and (2), when n is 2 or more, a plurality of k and q may be the same or different, respectively. Further, in the general formula (2), when n is 2 or more, a plurality of ts may be the same or different.

“K + q ≦ 4” in the annotation of the general formula (1) and “k + q + t ≦ 4” in the annotation of the general formula (2) are one phenol monomer part (a portion derived from the raw material phenols) located between the biphenylylene cross-linking groups. ) Shall be established.

Further, although j and s in the general formula (2) may be different numbers, they are preferably the same number. Similarly, l and u in the general formula (2) may be different numbers, but are preferably the same number. Further, in each of the n phenol monomer portions present in the general formula (2), k and t may be different numbers, but the same number is preferable.

In the general formula (1), at least one of j, k and l is 2, which means that the OA group among the benzene rings located at the end of the resin or between the biphenylylene cross-linking groups in the general formula (1) is It means that there is at least one benzene ring having two bonds. Similarly, in the general formula (2), at least one of j, k and l is 2, among the benzene rings located at the ends of the resin or between the biphenylylene cross-linking groups in the general formula (2). It means that there is at least one benzene ring to which two OH groups are bonded. In the general formula (1), the proportion of the benzene ring having two OA groups bonded to each benzene ring located at the end of the resin or between the biphenylylene cross-linking groups is the ratio of j, k and l in the formula (1). Of these, it is expressed as the ratio of j, k, and l, which are integers of 2. Similarly, in the general formula (2), the proportion of the benzene ring having two OH groups bonded to each benzene ring located at the end of the resin or between the biphenylylene cross-linking groups is j, k in the formula (2). And l are expressed as the ratio of j, k, and l, which are integers of 2. In any of the general formulas (1) and (2), the ratio of j, k and l, which is an integer of 2 among j, k and l, is 5% or more and 95% or less. It is preferable from the viewpoint of viscosity and heat resistance when it is made into a cured product. From this point of view, in any of the general formulas (1) and (2), the ratio of j, k and l, which are integers of 2, among j, k and l is 5% or more and 90% or less. It is preferably 5% or more and 80% or less, and particularly preferably.

In the general formulas (1) and (2), the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R may be linear, branched, or cyclic. Good. Specific examples of the saturated aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, iso-butyl group, amyl group and iso-amyl. Group, tert-amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, iso-heptyl group, Examples thereof include a tert-heptyl group, a 1-octyl group, an iso-octyl group, a tert-octyl group and an adamantyl group. 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. Be done. Examples of this unsaturated aliphatic hydrocarbon group include a group in which one or more of the carbon-carbon single bonds in each of the saturated aliphatic hydrocarbon groups mentioned above are replaced with a double bond or a triple bond. , Specifically, vinyl group, allyl group, isopropenyl group, 2-butenyl group, 2-methylallyl group, 1,1-dimethylallyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl. Linear or branched alkenyl groups such as groups, 4-pentenyl groups, hexenyl groups, octenyl groups, nonenyl groups, decenyl groups; alkynyl groups such as ethynyl groups, propa-2-in-1-yl groups; cyclobutenyl Cycloalkenyl groups such as groups, cyclopentenyl groups, cyclohexenyl groups, cycloheptenyl groups, cyclooctenyl groups, 4-methylcyclohexenyl groups, 4-ethylcyclohexenyl groups; polymers of acetylene, butadiene, isopropylene or copolymers thereof. Examples include a group consisting of. When the unsaturated aliphatic hydrocarbon group is an alkenyl group, it includes both a trans form and a cis form.

Examples of the aryl group represented by R include a phenyl group, a methylphenyl group, an ethylphenyl group, a naphthyl group, an anthrasenyl group and the like. 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, a phenethyl group and the like. 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 one having 1 to 10 carbon atoms, and examples thereof include a group corresponding to each saturated aliphatic hydrocarbon group mentioned above.

In the general formulas (1) and (2), Rs existing adjacent to each other on the same ring may be bonded to each other to form a fused ring. Examples of the fused ring formed in this case include naphthalene, anthracene, and phenanthrene.

The resin of the present invention preferably has an ICI viscosity at 150 ° C. of 5 Pa · s or less, preferably 3 Pa · s or less, from the viewpoint of successfully producing a semiconductor encapsulating material obtained by kneading with an inorganic filler or the like. It is more preferable that there is, and it is particularly preferable that it is 1 Pa · s or less. This viscosity can be measured by the method described in Examples described later.

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

The number average molecular weight Mn of the resin of the present invention is preferably 500 or more and 5000 or less, and more preferably 500 or more and 3000 or less. The number average molecular weight is measured by a GPC (Gel Permeation Chromatography) measuring device using a calibration curve made of standard polystyrene under the following devices and conditions.
GPC measuring device Model: Waters e2695
Column: LF-804
Measurement conditions Column pressure: 2.7 MPa
Eluent: THF flow rate 1 mL / min
Temperature: 40 ° C
Detector: Spectrophotometer (Waters 2489)
WAVE LENGTH: 254 nm and RI
Injection amount: 50 μL
Sample concentration: 5 mg / mL

The resin of the present invention can produce a cured product having a high glass transition temperature, excellent heat resistance, and excellent flame retardancy by reacting with a maleimide compound or the like, and exerts an effect difficult to obtain with a conventional phenol resin. is there.

The resin of the present invention can be suitably obtained by converting the biphenyl aralkyl novolak resin represented by the above general formula (I), which has a biphenylylene cross-linking group, into an allyl ether using allyl halides. Further, the allyl-modified biphenyl aralkyl novolac resin represented by the general formula (2) can be suitably obtained by heating the allyl ether-modified biphenyl aralkyl novolac resin of the general formula (1) and causing a Claisen rearrangement reaction. However, the resin of the present invention is not limited to those produced by these production methods.

The aralkyl novolak resin represented by the general formula (I) is not limited to the production method thereof, but an example of the production method of this resin will be described below.

[Manufacturing method of aralkyl novolak resin]
The aralkyl novolac resin represented by the general formula (I) is a compound represented by the following general formula (4) (for example, 4,4'-biphenylylene group, 2,4'-biphenylylene group, 2,2'-biphenylylene group, etc. A compound having (compound) and an excessive amount of phenols can be suitably produced by a one-step reaction by subjecting them to a condensation reaction in the presence of an acid catalyst or in the absence of a catalyst.

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

As the phenols, monohydric phenol, which is a compound having one hydroxyl group on the benzene ring, and divalent phenol, which is a compound having two hydroxyl groups on the benzene ring, are used in combination. Examples of monovalent phenols are phenol, cresol, ethylphenol, n-propylphenol, octylphenol, nonylphenol, phenylphenol, xylenol, methylpropylphenol, dipropylphenol, dibutylphenol, guayacol, guetor, trimethylphenol, naphthol, methyl. Examples thereof include naphthol, bisphenol, bisphenol A, bisphenol F, and allylphenol. These may be used alone or in combination of two or more. Of the monovalent phenols, preferred are phenols and cresols, and more preferred are phenols.

Examples of the divalent phenol include resorcin, hydroquinone, and catechol, and resorcin is preferable. These may be used alone or in combination of two or more.

The benzene ring of these phenols may have a substituent, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, or one or more substituted or unsubstituted aryl groups. May be good.

As a preferable mixing ratio of monovalent phenol and divalent phenol, the number of moles of divalent phenol is 5% or more when the total number of moles of the mixture of monovalent phenol and divalent phenol is 100%. It is preferably 95% or less, more preferably 5% or more and 90% or less, and particularly preferably 5% or more and 80% or less.

Examples of the compound (biphenyl-type cross-linking agent) represented by the general formula (4) include 4,4'-di (halogenomethyl) biphenyl, 2,4'-di (halogenomethyl) biphenyl, and 2,2'-di (halogeno). Methyl) biphenyl, 4,4'-di (alkoxymethyl) biphenyl, 2,4'-di (alkoxymethyl) biphenyl, 2,2'-di (alkoxymethyl) biphenyl, 4,4'-di (hydroxymethyl) Examples thereof include biphenyl, 2,4'-di (hydroxymethyl) biphenyl, 2,2'-di (hydroxymethyl) biphenyl and the like. 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 a chlorine atom is particularly preferable. The alkoxy group having 1 to 6 carbon atoms is not particularly limited, but one having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.

Preferred compounds represented by the general formula (4) include 4,4'-di (chloromethyl) biphenyl, 4,4'-di (methoxymethyl) biphenyl, and 4,4'-di (ethoxymethyl) biphenyl. Be done.

When the compound represented by the general formula (4) is reacted with phenols, it is preferable to use an acid catalyst. As the acid catalyst, organic acids such as oxalic acid, formic acid and acetic acid, and Friedelkraft type catalysts such as sulfuric acid, p-toluenesulfonic acid and diethyl sulfate can be preferably used. When a biphenyl-type cross-linking agent having a halogenomethyl group is used as the compound represented by the general formula (4), the reaction can be preferably carried out even in the absence of an acid catalyst.

By reacting the compound represented by the general formula (4) with a monovalent phenol and a divalent phenol in the presence or absence of an acid catalyst, the aralkyl novolac resin (aralkylene) of the general formula (I) is formed. Crosslinked phenol novolac resin) can be obtained. The monovalent phenol and the divalent phenol may be reacted as a mixture of two or more kinds, respectively. After completion of the reaction, the unreacted phenols can be distilled off from the system by heating under reduced pressure or while blowing an inert gas. In addition, the acid catalyst can be removed by washing such as washing with water.

[Manufacturing method of modified biphenyl aralkyl novolac resin]
The allyl ether-modified biphenyl aralkyl novolac resin represented by the general formula (1) of the present invention can be suitably obtained by subjecting the aralkyl novolak resin represented by the general formula (I) to an allylation reaction by a known method. .. As such a method, for example, a method of reacting an aralkyl novolak resin represented by the general formula (I) with allyl halide in the presence of a basic catalyst can be mentioned. As an example of a specific procedure, an organic solvent, a basic catalyst, and allyl halide such as allyl chloride are added to the aralkyl novolac resin represented by the general formula (I) as a raw material, and the hydroxyl group of the aralkyl novolac resin is allyl. (Allyl etherification).
The organic solvent, the basic catalyst and the allyl halide may be added to the resin at the same time or at different timings. When the organic solvent, the basic catalyst and the allyl halide are added at different timings, the organic solvent is added first, and then the allyl halide and the base are added. It is preferable to add the sex catalysts at the same time or either of them first.
As an example of a preferable means for allylating the allylate, a resin solution is obtained by dissolving the aralkylnovolac resin represented by the general formula (I) as a raw material in an organic solvent or the like, and then a basic catalyst is added to the resin solution. Then, allyl halide such as allyl chloride is added to allylate the hydroxyl group of the aralkylnovolac resin (allyl etherification). However, as described later, when the reaction is to be carried out "in the presence of undissolved sodium hydroxide", after mixing the raw material resin, the organic solvent and allyl halide, water is used as a basic catalyst for this mixture. It is also preferable to add sodium oxide.

Examples of the organic solvent used here include alcohols, ketones, nitrogen-containing aprotic polar solvents, sulfur-containing aprotic polar solvents and the like. Examples of alcohols include methanol, n-propanol, n-butanol and the like. Examples of the ketones include acetone, methyl ethyl ketone and the like. Examples of the nitrogen-containing aprotic polar solvent include polar solvents having a nitrogen atom in the molecule but not proticity, and examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-. Dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 1,3-diethyl-2-imidazolidinone. And so on. Examples of the sulfur-containing aprotic polar solvent include dimethyl sulfoxide and the like. Among these, a nitrogen-containing aprotic polar solvent is preferable from the viewpoint of obtaining the resin of the general formula (1) in a high yield and stably. Of these, it is preferable to use N, N-dimethylacetamide or N, N-dimethylformamide.

The amount of the organic solvent is not limited, but is preferably 50 parts by mass or more and 5000 parts by mass or less, and more preferably 100 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the resin of the general formula (I). It is preferable that virtually no water is used in this reaction. Specifically, the amount of water used is preferably less than 2% by mass and preferably 1% by mass or less with respect to the amount of the aralkyl novolak resin represented by the general formula (I) as a raw material.

Examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. The amount of the basic catalyst added is preferably 1.0 equivalent or more and 2.0 equivalent or less, and 1.0 equivalent or more and 1.5 equivalent or less with respect to the hydroxyl group of the aralkylnovolac resin represented by the general formula (I). It is more preferable that the amount is 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 novolak resin represented by the general formula (I) is sufficiently allylated, which is preferable. When it is 2.0 equivalent or less, unreacted water It is preferable because the residual amount of sodium oxide is suppressed and the removal step is facilitated.

One of the preferred embodiments of the aralkyl novolac resin represented by the general formula (I) is an aralkyl novolac resin in which R is a hydrogen atom and has no substituent other than a hydroxyl group.
The average value of the degree of condensation n of the aralkyl novolak resin, which is the preferred embodiment, is preferably 0.5 or more and 20.0 or less, and more preferably 2.0 or more and 10.0 or less. The degree of condensation n of the aralkyl novolak resin represented by the general formula (I) is such that the melt viscosity (ICI viscosity) at 150 ° C. is preferably 5 Pa · s or less, more preferably 3 Pa · s or less, still more preferably 1 Pa · s. The value is preferably s or less.
The hydroxyl group equivalent of the aralkylnovolac resin represented by the general formula (I) is preferably 100 g / eq or more and 400 g / eq or less, and more preferably 100 g / eq or more and 350 g from the viewpoint of successfully obtaining the resin of the present invention. It is / eq or less, and particularly preferably 100 g / eq or more and 300 g / eq or less.

As the allyl halide, allyl chloride, allyl bromide, allyl iodide and the like can be used. The amount of allyl halide added is preferably 1.0 equivalent or more and 2.0 equivalent or less, and more preferably 1.0 equivalent or more and 1.5 equivalent or less with respect to the basic catalyst. When the amount of allylation halide added is 1.0 equivalent or more, the progress rate of the allylation reaction can be set to a certain level or more, and when it is 2.0 equivalent or less, the raw material removal step is facilitated, which is preferable.

The temperature of the allylation reaction is not particularly limited, but it is preferably carried out at room temperature (25 ° C.) or higher and 100 ° C. or lower. When the temperature is set to room temperature or higher, the progress of the reaction can be kept above a certain level, and when the temperature is set to 100 ° C or lower, side reactions can be prevented from occurring and the desired allylated resin can be easily obtained, which is preferable. From this point of view, the more preferable temperature of the allylation reaction is 50 or more and 90 ° C. or less. The allylation reaction time is preferably 1 hour or more and 10 hours or less when the allylation reaction is carried out at room temperature (25 ° C.) or higher and 100 ° C. or lower, for example. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.

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

In the method for producing an allyl ether-modified biphenyl aralkylnovolak resin, one of the preferred embodiments is a reaction of a hydroxyl group of the biphenyl aralkylnovolak resin with allyl chloride (allyl etherification reaction) in a nitrogen-containing aprotic polar solvent under a nitrogen atmosphere. This is a production method in which undissolved sodium hydroxide is present in the solvent.
By performing the reaction "in the presence of undissolved sodium hydroxide", the step of newly dissolving the undissolved sodium hydroxide in the solvent controls the concentration of sodium hydroxide in the reaction solvent. Through the allyl etherification reaction, the reaction conditions are such that a certain concentration of sodium hydroxide is involved in the reaction, and the reaction can be carried out extremely mildly and stably.
The sodium hydroxide used in such a preferred embodiment is particles in which at least 80% by mass (preferably 90% by mass, more preferably 90 to 95% by mass) has a particle size of 0.5 mm or more in 100% by mass. Top or flaky sodium hydroxide is preferred. (Here, the "particle size" means the diameter when the spheres have the same volume even if they are in the form of particles or flakes). The particle size of sodium hydroxide at least 80% by mass is determined as follows. First, in a dry box under a dry nitrogen atmosphere, 20 g of sodium hydroxide is removed by sieving off those having a relatively small particle size using a sieve, and only those having a relatively large particle size are formed. 80% by mass or more of the sample is separated. From these separated samples, a plurality of samples having a relatively small particle size are visually selected, and each mass is measured, and the lightest sample is defined as having the smallest particle size. Using the mass of the smallest particle size and the density of sodium hydroxide (2.13 g / cm ³ ), the diameter when this sodium hydroxide is assumed to be a sphere is calculated. Then, it is assumed that the particle size of sodium hydroxide at least in 80% by mass is equal to or larger than the calculated diameter.
In addition, the above reaction conditions can be applied to the reaction conditions such as the amount of solvent and the reaction temperature.

Further, by heating the obtained allyl ether-modified biphenyl novolak resin represented by the general formula (1) and causing a Claisen rearrangement reaction, the allyl ether group is rearranged into a phenol nucleus, and the allyl modification represented by the general formula (2) is carried out. A biphenyl novolak resin can be obtained. The temperature of this rearrangement reaction is preferably 150 ° C. to 250 ° C., more preferably 180 ° C. to 230 ° C., and even more preferably 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, decomposition of raw materials and target substances can be more reliably prevented, and the desired allylic modification can be performed. It is preferable because a biphenyl novolak resin can be easily obtained. The Claisen rearrangement reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen.

The resin represented by the general formula (1) of the present invention and / or the resin represented by the general formula (2) of the present invention obtained above is a curing composition containing a maleimide compound, as will be described later. In addition, the resin represented by the general formula (2) of the present invention can be used as a curing agent for epoxy resins.

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

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

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

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

In the above general formulas (5) and (6), Y is −CR ¹ = CR ² − (R ¹ and R ² are independently hydrogen atoms or hydrocarbon groups having 1 or more and 5 or less carbon atoms). Is preferable. Further, Z can be a cyclic, linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, or a group in which two or more of these are combined.
s is preferably a value of 0 or more and 4 or less, and more preferably 0 or more and 2 or less.

Specific maleimide compounds include 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 1,6-bismamide- (2,4,4-trimethyl) hexane, and N, N'-decamethylene. An aliphatic (acyclic) such as bismaleimide, N, N'-octamethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-trimethylene bismaleimide, N, N'-ethylene bismaleimide. Although it may have a structure, bis [(2,5-dioxo-2,5-dihydropyrrole-1-yl) methyl] bicyclo [2,2,1] heptane, N, N'-p-phenylene bismaleimide , N, N'-m-phenylene bismaleimide, N, N'-2,4-toluylene bismaleimide, N, N'-2,6-toluylene bismaleimide, N, N'-4,4-diphenylmethane Bismaleimide, N, N'-3,3-diphenylmethane bismaleimide, N, N'-4,4 diphenyl ether bismaleimide, N, N'-3,3-diphenylether bismaleimide, N, N'-4 , 4-diphenylsulfide bismaleimide, N, N'-3,3-diphenylsulfide bismaleimide, N, N'-4,4-diphenylsulfone bismaleimide, N, N'-3,3-diphenylsulfone bismaleimide, N, N'-4,4-diphenylketone bismaleimide, N, N'-3,3-diphenylketone bismaleimide, N, N'-4,4-biphenyl bismaleimide, N, N'-3,3- Biphenylbismaleimide, N, N'-4,4-diphenyl-1,1-propanebismaleimide, N, N'-3,3-diphenyl-1,1-propanebismaleimide, 3,3'-dimethyl-N , N'-4,4-diphenylmethanebismaleimide, 3,3'-dimethyl-N, N'-4,4'-biphenylbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, bis [4- (3-Maleimidephenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidephenoxy) phenyl] ethane, 2,2- Bis [4- (3-maleimidephenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidephenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidephenoxy) phenyl] -1 , 1,1,3,3,3 -Hexafluoropropane, 4,4'-bis (3-maleimidephenoxy) biphenyl, bis [4- (3-maleimidephenoxy) phenyl] ketone, bis [4- (3-maleimidephenoxy) phenyl] sulfoxide, bis [4 The skeleton of the compound may have an aliphatic cyclic structure or an aromatic cyclic structure, such as − (3-maleimidephenoxy) phenyl] sulfone, bis [4- (3-maleimidephenoxy) phenyl] ether and the like. These bismaleimide compounds are used alone or in admixture of two or more.

The content of the maleimide compound in the composition of the present invention is the allyl of the allyl ether-modified biphenyl aralkylnovolac resin represented by the general formula (1) and / or the allyl-modified biphenyl aralkylnovolac resin represented by the general formula (2) of the present invention. The ratio of the number of base equivalents to the number of maleimide group equivalents of the maleimide compound [maleimide group equivalent number / allyl group equivalent number] is preferably in the range of 0.80 to 2.00, more preferably 0.80 to 1.60. Is the amount.
When this ratio is 0.80 or more, the heat resistance (glass transition temperature) and expandability (linear expansion rate) of the cured product are likely to be sufficient, which is preferable. Further, when this ratio is 2.00 or less, it becomes difficult to handle due to poor fluidity, which is a problem of conventionally known bismaleimide compounds, and it becomes difficult to cure at low temperature, and it can be obtained. This is preferable because the toughness of the cured product is lowered and defects such as brittleness are less likely to occur.

The number of functional group equivalents such as the number of maleimide group equivalents and the number of allyl group equivalents is B / A (corresponding) when the functional group equivalent of the compound is A (g / eq) and the charged amount is B (g). When the purity of the compound is C%, it can be determined by [B × C / 100] / A). That is, the functional group equivalents such as maleimide group equivalent and allyl group equivalent represent the molecular weight of the compound per functional group, and the functional group equivalent number is the number of functional groups (equivalent) per compound mass (charged amount). Represents a number).

The composition of the present invention can contain a curing accelerator. The curing accelerator may be any as long as it promotes the curing of the composition containing the maleimide compound and the allyl group-containing resin, and generally includes those used as a radical initiator. Examples of such a curing accelerator include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, peroxides having a t-butyl group, and peroxides having a cumyl group. Can be done. For example, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, capryl peroxide, lauroyl peroxide, acetyl peroxide, bis (1-hydroxycyclohexyl peroxide), Hydroxyheptyl peroxide, t-butyl hydroperoxide, p-methane hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide (sometimes abbreviated as DCPO), 2,5- Dimethyl-2,5-di (t-butyl peroxide) hexane, 2,5-dimethylhexyl-2,5-di (peroxybenzoate), t-butyl perbenzoate, t-butyl peracetate, t-butyl per acetate Organic peroxides such as octoate, t-butylperoxyisobutyrate, and di-t-butyl-di-perphthalate can be mentioned, and one of these may be used alone or in combination of two or more. be able to. When a curing accelerator is used, the amount added thereof is preferably 0.01 part by mass or more and 10 parts by mass or less, and 1 part by mass or more and 8 parts by mass with respect to 100 parts by mass of the resin of the present invention in the composition of the present invention. The following is more preferable.

In addition, the composition of the present invention may contain other optional components. As such an optional component, depending on the use of the composition of the present invention, for example, additives such as a filler, an imidazole compound for promoting curing, a coupling agent, a pigment, and a dye can be preferably used. Further, a solvent such as an organic solvent can also be used.

As the filler, either an organic filler or an inorganic filler can be used. As the inorganic filler, for example, amorphous silica, crystalline silica, alumina, calcium silicate, calcium carbonate, talc, mica, barium sulfate and the like can be used. In particular, it is preferable to use amorphous silica and crystalline silica. The particle size of the inorganic filler is not particularly limited, but it is preferably 0.01 μm or more and 150 μm or less in consideration of the filling rate. The blending ratio of the inorganic filler is not particularly limited, but the proportion of the inorganic filler in the maleimide composition is preferably 70% by mass or more and 95% by mass or less, and is 70% by mass or more and 90% by mass or less. More preferred. It is preferable to set the blending ratio of the inorganic filler in this range because the water absorption rate of the cured product of the composition is less likely to increase.

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. For example, when the composition of the present invention does not contain a filler, 10% by mass in the composition of the present invention. It is preferably 90% by mass or more, and more preferably 30% by mass or more and 60% by mass or less. Further, for example, when the composition of the present invention contains a filler, the amount of the resin of the present invention is preferably 5% by mass or more and 25% by mass or less, preferably 5% by mass or more and 20% by mass or less in the composition of the present invention. Is more preferable.

The amount of components other than the resin, maleimide compound, curing accelerator and filler of the present invention in the composition of the present invention varies depending on the use of the composition of the present invention, but generally.
It is preferably 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, the resin of the present invention, the maleimide compound, a curing accelerator added as needed, an inorganic filler, other additives, etc. are uniformly mixed using a mixer or the like. Then, the kneaded product may be kneaded in a molten state using a kneader such as a heating roll, a kneader or an extruder, the kneaded product may be cooled, and pulverized if necessary.

The composition of the present invention can be suitably cured by a conventional heat treatment. For example, the heat treatment is affected by the presence or absence of a radical initiator or curing accelerator, but is preferably 150 to 280 ° C, more preferably 150 to 250 ° C, preferably 1 to 24 hours, more preferably 1 to 12. It is preferable to carry out under normal pressure or under pressure using an autoclave or the like.

The resin of the present invention represented by the general formula (1) or (2) and the maleimide composition using the resin are not particularly limited, but are suitably used as a sealing material for sealing a semiconductor element. Can be done. For example, after installing a lead frame or the like on which the semiconductor element is mounted in a metal cavity, the maleimide composition is molded by a molding method such as a transfer mold, a compression mold, or an injection mold, and heated at a temperature of about 120 ° C. to 300 ° C. A semiconductor device can be suitably obtained by curing the composition by performing treatment or the like.

In addition, the composition of the present invention can preferably be uniformly dissolved in a known solvent such as methyl ethyl ketone, propylene glycol monomethyl ether, and dimethylformamide to produce a varnish solution. A prepreg for a printed circuit board can be produced by applying or impregnating the varnish solution to a porous glass substrate such as glass, glass fiber, paper, aramid fiber, or the like, and then heat-treating (semi-curing) the prepreg. Further, a laminated board in which a matrix resin is formed using the composition of the present invention is preferable by laminating a plurality of the obtained prepregs for a printed circuit board and performing heat treatment while pressurizing as necessary to cure the prepreg. Can be manufactured in.
Further, the laminated plate or prepreg can be obtained by superimposing a metal foil on one side or both sides and performing heat treatment while applying pressure as necessary to obtain a metal-clad laminated plate. This metal-clad laminate can be suitably used as a printed wiring board by forming a circuit pattern by etching treatment.

The resin of the present invention represented by the general formula (1) or (2) and the maleimide composition using the resin can be used for electrical and electronic parts such as a semiconductor element encapsulating material and a printed wiring board material, as well as a structure. It can be used as a material, adhesive, paint, etc. In particular, the resin of the present invention and the composition of the present invention make use of the characteristics of achieving both excellent flame retardancy and heat resistance, and make use of the characteristics of both excellent flame retardancy and heat resistance. It can be suitably used for parts, electronic parts used for display devices using high voltage, large batteries, and the like.

Needless to say, the present invention also provides a curing agent for maleimide resin containing the resin of the present invention represented by the above general formula (1) or (2), in addition to the resin and composition of the present invention. is there. The curing agent may consist only of the resin of the present invention, or may contain various additives in addition to the resin of the present invention. Examples of this additive include various components listed above as components other than the maleimide compound used in the composition of the present invention. The present invention also provides a method for curing a maleimide compound using the resin of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to these examples. Unless otherwise specified, "parts" indicates "parts by mass". Further, "%" indicates "mass%".

The evaluation method used in this example is shown below.
(1) Allyl group equivalent (eq / g): Measured by an iodine value titration method based on JIS K0070.
(2) Hydroxyl Equivalent (eq / g, hereinafter also referred to as “OH Equivalent”): Measured by hydroxyl group equivalent measurement according to JIS K0070.
(3) ICI Viscosity (Pa · s): MODEL CV-1S manufactured by TOA Corp. was used as the ICI cone plate viscometer. The plate temperature of the ICI viscometer was set to 150 ° C., and the sample was weighed in a predetermined amount. The weighed resin was placed on the plate, pressed with a cone from above, and left for 90 seconds. The cone was rotated and its torque value was read as ICI viscosity.
(4) Infrared absorption spectrum (IR) analysis The IR analysis of the resin was performed using a Fourier transform infrared spectrometer FT-IR analyzer Spectram manufactured by PerkinElmer.
(5) Glass transition temperature (Tg, ° C.): Measured using a thermomechanical analyzer (TMA-7100 manufactured by Hitachi, Ltd.) under the condition of a heating rate of 5 ° C./min.
(6) 5% mass reduction temperature (Td5) and heating mass reduction rate: Using TG / DTA (TG / DTA7200 manufactured by Hitachi High-Tech Science Corporation), 5% mass reduction under the condition of a temperature rise rate of 10 ° C./min. The mass loss rate at temperature (Td5) and 550 ° C. was measured.
(7) Flame retardancy: Evaluated according to UL-94. The burning time of each of the five test pieces was totaled to obtain the burning time.

[1] Preparation of allyl ether-modified biphenyl aralkyl novolac resin <Synthesis Example 1>
In a glass reaction kettle equipped with a stirrer, condenser, and nitrogen gas introduction tube, 315 g (3.4 mol) of phenol, 158.4 g (1.4 mol) of resorcin, 4,4'-di (chloromethyl) biphenyl. (Hereinafter, abbreviated as 4,4'-BCMB.) 200.8 g (0.8 mol) was charged and reacted at 100 ° C. for 3 hours.
Then, the temperature was raised to 160 ° C., and all 4,4'-BCMB were reacted. Meanwhile, the produced HCl was distilled off. After completion of the reaction, unreacted phenol and unreacted resorcin were distilled off by vacuum distillation to obtain a phenol novolac resin.
In the obtained phenol novolac resin, p, q and r are 0, j, k and l are independently 1 or 2, respectively, and the ICI viscosity (150 ° C.) is 0.70 Pa · in the general formula (I). It was a biphenyl aralkyl novolak resin (hereinafter referred to as raw material resin a) having a hydroxyl group equivalent of 136 (g / eq).
Further, when the divalent phenol introduction ratio in the resin is calculated from the amount of unreacted phenol distilled off and the amount of unreacted resorcin obtained by GPC analysis at the end of the reaction, the introduction ratio of divalent phenol (resorcin), that is, general The ratio of j, k and l, which are two integers of j, k and l in the formula (I), was 64%.

<Example 1>
In a four-necked flask equipped with a thermometer, a cooler, and a stirrer, 54.4 g (0.40 mol of hydroxyl group) of the raw material resin a obtained in Synthesis Example 1, 163.2 g of dimethylformamide, and 33.7 g of allyl chloride (allyl chloride). 0.44 mol) was added and dissolved uniformly. 16.8 g of sodium hydroxide (0.42 mol, having a particle size of at least 80% by mass (diameter when sodium hydroxide is assumed to be a sphere) is 4.3 mm or more) is added to this mixed solution as a basic catalyst. The allyl etherification reaction was carried out by reacting at 60 ° C. for 4 hours in a nitrogen atmosphere. The obtained reaction mixture was heated to 130 ° C. and unreacted allyl chloride and solvent were removed under reduced pressure. After lowering the temperature to 95 ° C., 150 g of methylisobutylketone was added to uniformly dissolve the mixture, and the mixture was washed 10 times with pure water to remove salts of by-products. After washing, the temperature was raised to 130 ° C. By removing the methylisobutylketone, the product resin A was obtained. The ICI viscosity of the resin A was measured, and the allyl group equivalent of the resin A was measured. These results are shown in Table 1 below. The table also shows the OH equivalent and the ICI viscosity of the raw material resin a. Further, the IR analysis of the raw material resin a and the resin A was performed by the above method. The IR analysis chart of the obtained raw material resin a is shown in FIG. The IR analysis chart of the resin A is shown in FIG.

As is clear from FIG. 2, in the chart of resin A, absorption of allyl ether was observed near 1200 cm ^-1 . In addition, absorption of carbon-carbon double bonds derived from the allyl group was observed near 900 cm ^-1 . On the other hand, the absorption of the phenolic hydroxyl group around 3400 cm- ¹ observed in the chart of the raw material resin a (FIG. 1) was 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 novolac resin represented by the general formula (1) in which the phenolic hydroxyl group of the raw material resin a is allyl etherified. Further, from the allyl group equivalent of the resin A, it was confirmed that almost all (90 mol% or more) of A in the general formula (1) were hydrogen atom-unsubstituted, that is, allyl groups. When calculating the ratio of allyl groups among A existing in the general formula (1), the number of A in the general formula (1) was regarded as the same as the number of OH groups in the raw material resin a.

[2] Preparation of allyl-modified biphenyl aralkyl novolac resin <Example 2>
The allyl etherified biphenyl aralkyl resin A obtained in Example 1 is added to a four-necked flask equipped with a thermometer, a cooler, and a stirrer, and a Claisen rearrangement reaction is carried out at 190 ° C. for 6 hours in a nitrogen atmosphere. Obtained the product resin B. The ICI viscosity of the resin B was measured. Moreover, the allyl group equivalent of the resin B was measured. These results are shown in Table 1 below. Further, IR analysis of the resin B was performed by the above-mentioned method. The obtained IR analysis chart is shown in FIG.

Similarly, as is clear from FIG. 3, the IR chart of resin B represented by FIG. 3 is around 1200 cm ^{-1 as} compared with the IR chart of resin A represented by the general formula (1) shown in FIG. The absorption of the allyl ether observed in the above was eliminated, and instead, the absorption of the phenolic hydroxyl group observed around 3400 cm ^-1 was significantly increased. Therefore, the resin A, which is the allyl ether-modified biphenyl aralkyl novolac resin represented by the general formula (1), has become the allyl-modified biphenyl aralkyl novolac resin represented by the general formula (2) by the Claisen rearrangement reaction. It was confirmed that the obtained resin B was a resin represented by the general formula (2). Further, from the allyl group equivalent of the resin B, it was confirmed that the ratio of the number of allyl groups to the number of OH groups in the general formula (2) was 90 mol% or more. In calculating this ratio, the number of OH groups in the general formula (2) was regarded as the same as the number of OH groups in the raw material resin a.

A maleimide composition was prepared using the modified biphenyl aralkyl novolac resin obtained in Examples 1 and 2, and the cured product properties of the cured product obtained from the maleimide composition were measured. The results are summarized in Table 2.

[3] Preparation and evaluation of maleimide composition or epoxy resin composition and cured product

<Example 3>
The allyl etherified biphenyl aralkyl novolac resin A obtained in Example 1 as a phenol resin, and the maleimide compound of BMI-1000 manufactured by Daiwa Kasei Kogyo Co., Ltd. (N, N'-4,4-diphenylmethanebismaleimide) (maleimide). A maleimide composition was prepared using an equivalent amount of 179 g / eq), dicumyl peroxide (DCPO) as a curing accelerator, and silica (MSR-2212) manufactured by Ryumori Co., Ltd. as a filler. Specifically, each of these components was mixed in the formulation shown in Table 2 below, kneaded with two rolls under a temperature condition of 80 ° C., and then pulverized to prepare a maleimide composition powder.
A test piece was prepared from a 40φ tablet prepared using the obtained maleimide composition powder by a transfer molding machine, and post-cured at 180 ° C. for 8 hours under normal pressure. The flame retardancy of the obtained cured product was evaluated by measuring the glass transition temperature, 5% mass reduction temperature (Td5), and heating mass reduction rate by the above method.

<Example 4>
Using the allylated biphenyl aralkyl resin B obtained in Example 2 as the phenol resin, a cured product was obtained in the same manner as in Example 3 except that the maleimide composition was prepared by the formulation shown in Table 2 below, and the temperature was reduced by 5%. (Td5) and the heating mass reduction rate were measured to evaluate the flame retardancy.

<Comparative example 1>
The phenolic resin is an allylphenol novolak resin represented by the following general formula (7), which is liquid at room temperature (25 ° C.) (E-type viscosity (25 ° C.):
1770 mPa · s), number average molecular weight Mn: 400, hydroxyl group equivalent 144 g / eq, allyl group equivalent 144 g / eq. A cured product was obtained in the same manner as in Example 3 except that the maleimide composition was prepared by the formulation shown in Table 2 below using (hereinafter, also referred to as resin X), and the 5% mass reduction temperature (Td5) and the heating mass reduction rate were measured. It was measured and flame retardancy was evaluated.

<Comparative example 2>
As the phenol resin, a triphenylmethane type phenol resin represented by the following general formula (8) (ICI viscosity (150 ° C.): 0.9 Pa · s) and a number average molecular weight Mn: 530 (hereinafter also referred to as resin Y) were used. Triphenylmethane type epoxy resin EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, triphenylphosphine (sometimes abbreviated as TPP) as a curing accelerator, and silica manufactured by Ryumori Co., Ltd. (MSR-) as a filler. 2212) was used to prepare a highly heat resistant EMC composition. Specifically, each of these components was mixed in the formulation shown in Table 2, kneaded with two rolls under a temperature condition of 80 ° C., and then pulverized to prepare an EMC powder.
A 40φ tablet prepared by using the obtained EMC powder was prepared as a test piece by a transfer molding machine, and post-cured at 180 ° C. for 8 hours under normal pressure. The flame retardancy of the obtained cured product was evaluated by measuring the glass transition temperature, 5% mass reduction temperature (Td5), and heating mass reduction rate by the above method.

As shown in Table 2, it can be seen that the maleimide compositions of Examples 3 and 4 using the modified biphenyl aralkyl novolac resins A and B of the present invention have high heat resistance and excellent flame retardancy. .. On the other hand, the maleimide composition of Comparative Example 1 using the resin X, which is an allyl-modified phenolic resin different from the resin of the present invention, is significantly inferior to Examples 3 and 4 in terms of flame retardancy and has heat resistance. In this respect as well, it can be seen that the items of Td5 and the heating mass reduction rate are inferior. Further, the epoxy resin composition of Comparative Example 2 using the resin Y, which is a phenol resin different from the resin of the present invention, is significantly inferior to Examples 3 and 4 in terms of flame retardancy, and further, in terms of heat resistance. It can be seen that all the items of Tg, Td5 and the heating mass reduction rate are significantly inferior to those of Examples 3 and 4.

Claims (10)

A method for producing an allyl ether-modified biphenyl aralkyl novolac resin represented by the following general formula (1).
(During the ceremony
A indicates an allyl group and
R represents 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 from each other.
j, k, and l each independently represent an integer of 1 to 2.
However, at least one of j, k and l is 2.
p, q and r independently represent integers 0 to 3, respectively.
k + q ≦ 4
n represents a value from 0 to 20.
However, some of the allyl groups represented by A may be substituted with hydrogen atoms. )
A method for producing an allyl ether-modified biphenyl aralkyl novolak resin, in which the aralkyl novolac resin represented by the following general formula (I) is reacted with allyl halide in the presence of a basic catalyst under the condition that water is not substantially used.
(During the ceremony
R represents 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 from each other.
j, k, and l each independently represent an integer of 1 to 2.
However, at least one of j, k and l is 2.
p, q and r independently represent integers 0 to 3, respectively.
k + q ≦ 4
n represents a value from 0 to 20. ) The allyl-modified biphenyl aralkyl novolac resin represented by the following general formula (2) that transfers the allyl ether-modified biphenyl aralkyl novolac resin represented by the above general formula (1) produced by the production method according to claim 1 to Claisen rearrangement. Production method.
(During the ceremony
A indicates an allyl group and
R represents 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 from each other.
j, k, and l each independently represent an integer of 1 to 2.
However, at least one of j, k and l is 2.
p, q and r independently represent integers 0 to 3, respectively.
s, t and u each independently represent an integer of 0 to 2.
j + p + s ≦ 5, k + q + t ≦ 4, and l + r + u ≦ 5.
n represents a value from 0 to 20.
However, s, t and u are never 0. ) The method for producing an allyl ether-modified biphenyl aralkyl novolac resin according to claim 1, wherein a nitrogen-containing aprotic polar solvent is used. The allyl ether-modified biphenyl aralkyl novolac resin obtained by the production method according to claim 1 and / or the allyl-modified biphenyl aralkyl novolac resin obtained by the production method according to claim 2 contains two or more maleimide groups in one molecule. A method for producing a composition in which a compound having a compound is blended. The method for producing a composition according to claim 4, which contains a curing accelerator. The method for producing a composition according to claim 4 or 5, wherein the filler is contained. A method for producing a cured product from a composition obtained by the production method according to any one of claims 4 to 6. A method for producing a sealing material for a semiconductor device from a composition obtained by the production method according to any one of claims 4 to 6. A method for manufacturing a semiconductor device sealed by using the sealing material obtained by the manufacturing method according to claim 8 . A method for producing a laminated board using the composition obtained by the production method according to any one of claims 4 to 6 as a matrix resin.