JP2022157197A - Active ester, curable resin composition, and cured product - Google Patents

Abstract

To provide an active ester which gives a cured product that can exhibit high heat resistance, low dielectric characteristics (low dielectric constant and low dielectric loss tangent), and high elastic modulus, a curable resin composition containing the active ester, a cured product obtained using the curable resin composition, and a circuit board using the curable resin composition.SOLUTION: An active ester is obtained by reacting an aromatic compound (a) having two hydroxyl groups at adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound having two or more carboxyl groups and/or its acid halide or esterified product (c).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an active ester, a curable resin composition containing the active ester, and a cured product obtained from the curable resin composition.

Epoxy resin compositions, which contain epoxy resins and their curing agents as essential components, exhibit excellent heat resistance and insulating properties in their cured products, and are therefore widely used in electronic component applications such as semiconductors and multilayer printed circuit boards. .

Among these electronic component applications, semiconductor package substrates are becoming thinner, but warping of the package substrate during mounting has become a problem. A high elastic modulus is required.

On the other hand, in recent years, even in semiconductor package substrates, signals are becoming faster and higher in frequency. It is desired to provide a curable resin composition capable of obtaining a cured product exhibiting a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for high-speed, high-frequency signals. ing.

In response to these demands, there is known a technique of using an active ester compound as a curing agent for epoxy resin as a material capable of realizing a low dielectric constant and a low dielectric loss tangent (see Patent Document 1).

However, in Patent Document 1, the characteristics of low dielectric constant and low dielectric loss tangent are insufficient to meet the recent demands, and the heat resistance also does not satisfy the demands. In addition, in order to cope with miniaturization and thinning, high elastic modulus is required.

JP-A-2004-169021

Therefore, the problem to be solved by the present invention is that the resulting cured product exhibits high heat resistance, low dielectric properties (low dielectric constant and low dielectric loss tangent), and an active ester capable of expressing a high elastic modulus, An object of the present invention is to provide a curable resin composition containing an active ester, a cured product obtained using the curable resin composition, and a circuit board using the curable resin composition.

Therefore, the inventors of the present invention have made intensive studies to solve the above problems, and found that by using a specific active ester in a curable resin composition, the obtained cured product has excellent high heat resistance and low dielectric strength. The present inventors have found that it exhibits properties (low dielectric constant and low dielectric loss tangent) and high elastic modulus, and have completed the present invention.

That is, the present invention provides an aromatic compound (a) having two hydroxyl groups at adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound having two or more carboxyl groups and/or or its acid halide or ester (c).

（上記式中、Ｒは、それぞれ独立に、炭素原子数１～１０の炭化水素基を表し、ｎは０～４の整数を表し、ｍは０～２の整数を表す。） In the active ester of the present invention, the aromatic compound (a) is preferably at least one compound selected from the group consisting of general formulas (1) to (3) below.

(In the above formula, each R independently represents a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 4, and m represents an integer of 0 to 2.)

The present invention relates to a curable resin composition containing the active ester and an epoxy resin.

The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.

TECHNICAL FIELD The present invention relates to a prepreg comprising a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material.

The present invention relates to a circuit board characterized by being obtained by laminating the prepreg and copper foil, followed by thermocompression molding.

The present invention relates to a build-up film containing the curable resin composition.

The present invention relates to a semiconductor sealing material containing the curable resin composition.

The present invention relates to a semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material.

According to the present invention, an active ester capable of exhibiting excellent high heat resistance, low dielectric properties (low dielectric constant and low dielectric loss tangent), and high elastic modulus in the resulting cured product, and curing containing the active ester curable resin composition, and a cured product obtained using the curable resin composition, and further, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, and a build using the curable resin composition It is useful because it can provide an up film and the like.

[Active ester]
The present invention provides an aromatic compound (a) having two hydroxyl groups at adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound having two or more carboxyl groups and/or its It relates to an active ester characterized by being obtained by reacting with an acid halide or ester (c).
By using the active ester, a cured product having high heat resistance, low dielectric properties (low dielectric constant, low dielectric loss tangent) and high elastic modulus can be obtained, which is preferable. The reason why such properties are obtained is not necessarily clear, but by using an aromatic compound (a) (e.g., catechol) having two hydroxyl groups at adjacent positions on the aromatic ring as a raw material for the active ester. , an ester group based on two hydroxyl groups of the aromatic compound (a) having two hydroxyl groups at adjacent positions on the aromatic ring is formed at adjacent positions of the aromatic ring (e.g., benzene ring), and the cured product High heat resistance and high elastic modulus are exhibited by adjacent cross-linking points and inhibition of molecular movement due to steric hindrance. In addition, since the active ester reacts with the epoxy resin and can form a network structure without a secondary hydroxyl group, which is a polar group, a sufficiently low dielectric constant and dielectric loss tangent can be exhibited.

[Aromatic compound (a) having two hydroxyl groups at adjacent positions on the aromatic ring]
The active ester of the present invention is obtained by reacting an aromatic compound (a) having two hydroxyl groups at adjacent positions on the aromatic ring (hereinafter sometimes referred to as "aromatic compound (a)"). It is characterized by The above-mentioned "two hydroxyl groups at adjacent positions on the aromatic ring" means "two hydroxyl groups bonded to two adjacent carbon atoms on the aromatic ring".

Further, in the active ester of the present invention, the aromatic compound (a) is preferably at least one compound selected from the group consisting of the following general formulas (1) to (3). Since the compound has hydroxyl groups adjacent to each other on the aromatic ring, the ester groups contained in the obtained active ester are also adjacent to each other, and the cross-linking points of the cured product obtained using the active ester are adjacent to each other. High heat resistance and high elastic modulus can be exhibited by hindering molecular motion due to steric hindrance, which is preferable.

In the above formulas (1) to (3), R is preferably each independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group includes a methyl group, an ethyl group, a propyl group, Examples include a butyl group, an allyl group, and a benzyl group, and from the viewpoint of high heat resistance and low dielectric loss tangent, it is preferably unsubstituted, and from the viewpoint of a low dielectric constant, it is preferably a butyl group. preferable.

In the above formulas (1) to (3), n is preferably an integer of 0-4, more preferably an integer of 0-1. When n is within the above range, high heat resistance, low dielectric loss tangent, and low dielectric constant are obtained, which is preferable.

In the above formulas (1) to (3), m is preferably an integer of 0-2, more preferably an integer of 0-1. When m is within the above range, high heat resistance, low dielectric loss tangent, and low dielectric constant are obtained, which is preferable.

In addition, as the aromatic compound (a), it is preferable to use a compound containing a catechol skeleton (catechol compound), and more specifically, a catechol compound such as catechol or tert-butyl catechol is more preferable. The obtained cured product can have high heat resistance, low dielectric properties (low dielectric constant, low dielectric loss tangent) and high elastic modulus, which is preferable. By introducing a catechol skeleton based on the aromatic compound (a) into the active ester, the ester groups in the active ester form a structure adjacent to each other on the same aromatic ring. As a result, steric hindrance is increased, molecular motion is suppressed, and the resulting cured product has low dielectric properties (low dielectric constant and low dielectric loss tangent) and can be made high in elastic modulus. In addition, since the active ester reacts with the epoxy resin and can form a network structure without a secondary hydroxyl group that is a polar group, the resulting cured product exhibits a sufficiently low dielectric constant and dielectric loss tangent. be able to.

The catechol is a dihydroxybenzene having hydroxyl groups at the 1- and 2-positions, and may be a catechol compound having an alkyl group such as a methyl group as a substituent on the aromatic ring of the catechol.

As the catechol compound, it is preferable to use a compound having no substituent on the aromatic ring (for example, catechol) from the viewpoint of imparting high heat resistance. From the viewpoint of low dielectric properties, catechol compounds having alkyl groups with 4 to 10 carbon atoms, such as catechol having a tertiary butyl group (tertiary butyl catechol), are used as the catechol compound. preferably. When the number of carbon atoms is 4 or more, sufficient low dielectric properties can be obtained, and when the number of carbon atoms is 10 or less, a decrease in reactivity due to steric hindrance during synthesis of an active ester can be prevented, which is preferable. .

The aromatic compound (a) may be used alone, or may be used in combination with a plurality of compounds having different positions of alkyl groups such as methyl groups.

[Aromatic monohydroxy compound (b)]
The present invention is characterized by being obtained by reacting the aromatic monohydroxy compound (b). By using the aromatic monohydroxy compound (b), the active ester obtained is such that the aromatic monohydroxy compound (b) serves as a terminal blocking agent during the synthesis of the active ester, controls the molecular weight distribution, and the active ester can be optimized.

The aromatic monohydroxy compound (b) is not particularly limited, but examples include alkylphenols such as phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, and tertiary butylphenol. aralkylphenols such as o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol, 4-(α-cumyl)phenol; α-naphthol (1-naphthol), β-naphthol Naphthol compounds such as (2-naphthol) can be mentioned. Each of these may be used alone, or two or more of them may be used in combination. Among them, tertiary butyl phenol, α-naphthol, and the like are preferable because a cured product having excellent heat resistance and dielectric properties (low dielectric properties) can be obtained.

[Aromatic compound having two or more carboxyl groups and/or its acid halide or ester (c)]
In the present invention, an aromatic compound having two or more carboxyl groups and/or its acid halide or ester (c) (hereinafter sometimes referred to as "aromatic compound etc. (c)") is reacted. It is characterized by being obtained by By using the aromatic compound (c), etc., a cured product having excellent heat resistance can be obtained, which is preferable.

The aromatic compound (c) is not particularly limited, but examples thereof include compounds having two or more carboxyl groups in a substituted or unsubstituted aromatic ring. The term "carboxyl group, etc." means a carboxyl group; an acyl fluoride acyl group, an acyl chloride group, an acyl bromide group; an alkyloxycarbonyl group such as a methyloxycarbonyl group, an ethyloxycarbonyl group; aryloxycarbonyl groups such as oxycarbonyl group and naphthyloxycarbonyl group; When having an acyl halide group, the aromatic compound is an acid halide, and when having an alkyloxycarbonyl group or an aryloxycarbonyl group, the aromatic compound can be an ester. Among these, the aromatic compound preferably has a carboxyl group, a halogenated acyl group, an aryloxycarbonyl group, more preferably has a carboxyl group, a halogenated acyl group, a carboxyl group, an acyl chloride group, a brominated It is more preferable to have an acyl group.

Examples of the aromatic ring include, but are not particularly limited to, a monocyclic aromatic ring, a condensed aromatic ring, a ring-assembled aromatic ring, and an aromatic ring linked by an alkylene chain.

The aromatic compounds (c) are not particularly limited, but are benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; trimellitic acid, 5-allyltrimellitic acid, and the like. benzenetricarboxylic acid of; naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalenedicarboxylic acids such as 3-allylnaphthalene-1,4-dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; triazinecarboxylic acids such as 5-triazine-2,4,6-tricarboxylic acid; and acid halides and esters thereof. Among these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarbonyl Trichloride is more preferable, and bis(chlorocarbonyl)benzene such as isophthalic acid chloride and terephthalic acid chloride, and 1,3,5-benzenetricarbonyl trichloride are more preferred.

Among the above, from the viewpoint of improving the heat resistance and dielectric properties of the resulting cured product, and from the viewpoint of industrial availability and workability of raw materials, aromatic compounds in which the aromatic ring is a monocyclic aromatic ring, etc. Aromatic compounds in which the aromatic ring is a condensed aromatic ring are preferable, and benzenedicarboxylic acid, benzenetricarboxylic acid, naphthalenedicarboxylic acid, and acid halides thereof are preferable, and benzenedicarboxylic acid, naphthalenedicarboxylic acid, These acid halides are more preferred, and isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7 -dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, and acid halides thereof are more preferred. The above-mentioned aromatic compounds and the like (c) may be used alone or in combination of two or more.

The active ester of the present invention has a function as a curing agent for epoxy resins and the like, and the cured product obtained by using the active ester has high heat resistance, low dielectric properties (low dielectric In addition, a high elastic modulus can be imparted, which is a preferred embodiment. In addition, during the reaction between the active ester and the epoxy resin, it is possible to prevent or suppress the generation of hydroxyl groups, which is excellent in low dielectric properties and useful.

By using the active ester of the present invention, a cured product having low dielectric properties, high heat resistance, and excellent elastic modulus can be obtained, which is a preferred embodiment. The reason for this is not necessarily clear, but by introducing a catechol skeleton based on the aromatic compound (a) into the active ester, the ester groups in the active ester have a structure in which they are adjacent on the same aromatic ring. Therefore, steric hindrance is increased and molecular motion is suppressed compared to conventional designs, and the resulting cured product has low dielectric properties (low dielectric constant, low dielectric loss tangent) and high elastic modulus. In addition, since the active ester reacts with the epoxy resin and can form a network structure without a secondary hydroxyl group, which is a polar group, a sufficiently low dielectric constant and dielectric loss tangent can be developed.

In addition, since the active ester has two or more ester bonds reactive with the epoxy group of the epoxy resin to be described later, the crosslink density of the cured product can be increased and the heat resistance can be improved.

As the active ester, the softening point of the active ester is 200 ° C. or less from the viewpoint of better balance between handling properties when preparing a curable resin composition described later, heat resistance of the cured product, and dielectric properties. is preferably 180° C. or lower, more preferably 160° C. or lower, and particularly preferably 140° C. or lower.

The reaction with the aromatic compound (a), the aromatic monohydroxy compound (b), and the aromatic compound (c) (hereinafter sometimes referred to as "raw material compound") is particularly limited However, for example, after mixing and dissolving the aromatic compound (a) and the aromatic monohydroxy compound (b), the aromatic compound (c) is further mixed and dissolved, and the alkali catalyst is The reaction can be carried out in the presence of 60° C. or lower for a reaction time of 1 to 24 hours. Examples of alkali catalysts that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. Each of these may be used alone, or two or more of them may be used in combination. Among these, sodium hydroxide or potassium hydroxide is preferable because of their high reaction efficiency. Also, these catalysts may be used as an aqueous solution of 3 to 30% by mass. Moreover, in this case, an interlayer transfer catalyst may be used in order to increase the reaction efficiency. Examples include alkylammonium salts, crown ethers, and the like. Each of these may be used alone, or two or more of them may be used in combination.

The above reaction is preferably carried out in an organic solvent because it facilitates reaction control. Examples of organic solvents used here include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether. Examples thereof include acetic acid ester solvents such as acetate and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Each of these may be used alone, or two or more of them may be used as a mixed solvent.

The reaction ratio of the raw material compound can be appropriately changed according to the desired molecular design. The amount of the aromatic compound (a) is preferably 0.5 to 5 mol, more preferably 1 to 4 mol, even more preferably 2 to 3 mol, per 1 mol of (b). Further, the aromatic compound (c) is preferably in the range of 0.5 to 5 mol, more preferably 1 to 4 mol, and further 2 to 3 mol, relative to 1 mol of the aromatic monohydroxy compound (b). preferable.

After completion of the reaction, when an aqueous solution is used in the presence of an alkali catalyst, the reaction solution is allowed to stand for liquid separation to remove the aqueous layer, the remaining organic layer is washed with water, and the aqueous layer is almost neutral (pH 7). The active ester of the present invention can be obtained by repeating washing with water until the content of the inorganic salt, which adversely affects the insulating properties, is reduced. After completion of the reaction, in order to remove the surplus raw material compound, the active ester of high purity can be obtained by drying under heating and reduced pressure.

The functional group equivalent of the active ester of the present invention is, when the total number of aromatic ester groups in the active ester structure is taken as the number of functional groups of the active ester, excellent curability, low dielectric constant and dielectric loss tangent (low dielectric characteristics). Since a cured product can be obtained, it is preferably in the range of 100 to 500 g/equivalent, more preferably in the range of 110 to 400 g/equivalent, and even more preferably in the range of 120 to 300 g/equivalent.

The number average molecular weight (Mn) of the active ester of the present invention is preferably 500-3000, more preferably 600-2000. A number-average molecular weight (Mn) of 500 or more is preferable because dielectric properties and heat resistance are excellent. On the other hand, when the number average molecular weight (Mn) is 3000 or less, it is preferable because moldability is excellent.

<Curable resin composition>
The present invention relates to a curable resin composition containing the active ester and an epoxy resin. In the curable resin composition, the active ester functions as a curing agent for epoxy resins (and other resins), and the cured product obtained by using the active ester and the epoxy resin is High heat resistance, low dielectric properties (low dielectric constant, low dielectric loss tangent), and high elastic modulus can be achieved, which is a preferred embodiment. Moreover, it is possible to prevent or suppress the generation of hydroxyl groups during the reaction between the active ester and the epoxy resin, and to obtain a cured product excellent in low dielectric properties, which is useful.

[Epoxy resin]
Although the epoxy resin is not particularly limited, for example, it is preferably a curable resin that contains two or more epoxy groups in the molecule and can be cured by forming a crosslinked network with the epoxy groups.

The epoxy resin is not particularly limited, but phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl novolak type epoxy resin. Novolac type epoxy resins such as resins;
Aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins;
Bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as tetrabromobisphenol A type epoxy resin;
Biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton;
Naphthalene type epoxy resin;
Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin;
Dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin;
Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins, triglycidyl-p-aminophenol type epoxy resins, diaminodiphenylsulfone glycidylamine type epoxy resins;
diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins;
Examples include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran.
Among these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing phenolic compounds are preferred. is more preferable from the viewpoint of

The epoxy resins described above may be used alone or in combination of two or more.

The epoxy equivalent weight of the epoxy resin is preferably 120-400 g/equivalent, more preferably 150-350 g/equivalent. When the epoxy equivalent of the epoxy resin is 120 g/equivalent or more, it is preferable because the dielectric properties of the resulting cured product are excellent. It is preferable because it has an excellent balance between the properties and the dielectric loss tangent.

The softening point of the epoxy resin is preferably 20 to 200°C, more preferably 40 to 150°C. It is preferable that the softening point of the epoxy resin is 20° C. or higher because it can also have rapid curability. On the other hand, when the softening point of the epoxy resin is 200° C. or lower, it is preferable because the moldability is excellent.

The functional group (ester group) equivalent ratio (active ester/epoxy resin) of the amount of the active ester used to the amount of the epoxy resin used is preferably 0.1 to 5, and preferably 0.5 to 4. is more preferred. When the functional group equivalent ratio is within the range, the curability of the curable resin composition is further improved, the dielectric loss tangent of the resulting cured product is further reduced, and the heat resistance is further improved, which is preferable.

In addition to the active ester and epoxy resin, the curable resin composition of the present invention further contains other curing agents, other resins, solvents, additives, etc., within a range that does not impair the effects of the present invention. You can

[Other curing agents]
In the curable resin composition of the present invention, other curing agents may be used together with the active ester.

Examples of other curing agents include, but are not limited to, amine curing agents, acid anhydride curing agents, phenolic resin curing agents, and the like.

The amine curing agent is not particularly limited, but diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethyl Aliphatic amines such as piperazine, mensenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N'-dimethylpiperazine, triethylenediamine; m-xylylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethyl and aromatic amines such as aminomethyl)phenol.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tri trimellitate, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexenedicarboxylic anhydride.

Examples of the phenol resin curing agent include phenol novolak resin, cresol novolak resin, naphthol novolak resin, bisphenol novolak resin, biphenyl novolak resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, and triphenol methane type resin. , tetraphenol ethane type resin, aminotriazine-modified phenol resin, and the like.

The above other curing agents may be used alone or in combination of two or more.

[Other resins]
The curable resin composition of the present invention may contain other resins in addition to the epoxy resin. In addition, in this specification, "another resin" means resins other than an epoxy resin.

Specific examples of the other resins are not particularly limited, but maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate esters. Examples include resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphates, and phosphate-carbonate copolymers. These other resins may be used alone or in combination of two or more.

[solvent]
The curable resin composition of the present invention may be prepared without solvent or may contain a solvent. The solvent has a function of adjusting the viscosity of the curable resin composition.

Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl. ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene Examples include aromatic hydrocarbons, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the curable resin composition. It is preferable that the amount of the solvent used is 10% by mass or more because the handleability is excellent. On the other hand, it is preferable from the viewpoint of economy that the amount of the solvent used is 90% by mass or less.

[Additive]
The curable resin composition of the present invention may contain additives. Examples of the additives include curing accelerators, flame retardants, fillers, and the like.

(Curing accelerator)
Examples of the curing accelerator include, but are not limited to, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators.

Examples of the phosphorus curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripparatolylphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphine compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Examples include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo [5. 4.0]-undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN) and the like.

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2 -methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.

Examples of the urea curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1 -dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea and the like.

Among the curing accelerators mentioned above, 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP) are preferably used.

In addition, the above curing accelerators may be used alone or in combination of two or more.

The amount of the curing accelerator used can be appropriately adjusted in order to obtain the desired curability, but it is 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin and the active ester. is preferred, and 0.1 to 3 parts by mass is more preferred. It is preferable that the amount of the curing accelerator used is 0.01 parts by mass or more because the curability is excellent. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, the insulation reliability is excellent, which is preferable.

(Flame retardants)
The flame retardant is not particularly limited, but includes inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like.

Examples of the inorganic phosphorus-based flame retardant include, but are not particularly limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; and phosphate amides.

The organic phosphorus flame retardant is not particularly limited, but methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butylpyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) Phosphate esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphine Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 Cyclic phosphorus compounds such as -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; Aldehyde compounds, compounds obtained by reacting with phenol compounds, and the like.

The halogen-based flame retardant is not particularly limited, but brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4 ,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid and the like.

The above flame retardants may be used alone or in combination of two or more.

The amount of the flame retardant used is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the epoxy resin. It is preferable that the amount of the flame retardant used is 0.1 parts by mass or more because flame retardancy can be imparted. On the other hand, when the amount of the flame retardant used is 50 parts by mass or less, it is preferable because flame retardancy can be imparted while maintaining dielectric properties.

(filler)
Examples of fillers include organic fillers and inorganic fillers. The organic filler has a function of improving elongation, a function of improving mechanical strength, and the like. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and imparting flame retardancy.

Examples of the organic filler include, but are not particularly limited to, polyamide particles.

The inorganic filler is not particularly limited, but silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, nitride Boron, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate , calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like. Among these, it is preferable to use silica. At this time, as silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like can be used.

Moreover, the filler may be surface-treated as necessary. At this time, the surface treatment agent that can be used is not particularly limited, but aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based cups. A ring agent or the like may be used. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldimethoxysilane, silazane and the like.

In addition, the above fillers may be used alone or in combination of two or more.

The amount of the filler used is preferably 0.5 to 95 parts by mass, more preferably 5 to 80 parts by mass, based on 100 parts by mass of the epoxy resin. It is preferable that the amount of the filler used is 0.5 parts by mass or more because the effect of the filler can be sufficiently imparted. On the other hand, the amount of the filler used is preferably 95 parts by mass or less so as not to impair the moldability due to an increase in the viscosity of the compound.

<Cured product>
The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction. Since the active ester itself has a low dielectric loss tangent, the cured product obtained from the curable resin composition containing the active ester also has a low dielectric loss tangent. This is a preferred embodiment because it is possible to exhibit properties and high elastic modulus due to suppression of warpage.

As a method for obtaining a cured product obtained by subjecting the curable resin composition to a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is 100 to 300 ° C., and the heating time is 1 to 300 ° C. 24 hours is preferred.

<Application of curable resin composition>
Applications for which the curable resin composition is used include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as build-up adhesive films, resin injection Mold materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, molded articles obtained by curing the above composite materials, and the like. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive film applications for build-ups are used for so-called electronic component built-in substrates in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. can be used as an insulating material for Furthermore, among the above, the curable resin composition of the present invention can be used as a semiconductor encapsulating material, a semiconductor device, and a prepreg by taking advantage of the properties that the cured product has excellent heat resistance, low dielectric properties, and a high elastic modulus. , flexible wiring boards, circuit boards, build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and moldings obtained by curing the above composite materials. A method for producing the semiconductor encapsulating material and the like from the curable resin composition will be described below.

1. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor sealing material containing the curable resin composition. As a method for obtaining a semiconductor encapsulating material from the curable resin composition, the curable resin composition, a curing accelerator, and compounding agents such as inorganic fillers are optionally extruded, kneaded, A method of sufficiently melting and mixing using a roll or the like until uniform is exemplified. At that time, fused silica is usually used as the inorganic filler, but when it is used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and nitride, which have higher thermal conductivity than fused silica, are used. High filling of silicon or the like, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. The filling rate is preferably in the range of 30 to 95 parts by weight of the inorganic filler per 100 parts by weight of the curable resin composition. is more preferably 70 parts by mass or more, and more preferably 80 parts by mass or more.

2. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material. As a method of obtaining a semiconductor device from the above curable resin composition, the above semiconductor encapsulating material is molded using a casting mold, a transfer molding machine, an injection molding machine, or the like, and further cured at 50 to 200° C. for 2 to 10 hours. a method of heating for a while.

3. TECHNICAL FIELD The present invention relates to a prepreg comprising a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material. As a method for obtaining a prepreg from the curable resin composition, the curable resin composition obtained by blending the following organic solvent to form a varnish is applied to a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) and then heating at a heating temperature according to the type of solvent used, preferably at 50 to 170°C. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to 20 to 60% by mass.

Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. Although it can be appropriately selected depending on the application, for example, when further manufacturing a printed circuit board from a prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, or dimethylformamide. , the non-volatile content is preferably 40 to 80% by mass.

4. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circuit board obtained by laminating the prepreg and copper foil, and thermocompression molding. As a method for obtaining a printed circuit board from the curable resin composition, the prepreg is laminated by a conventional method, copper foil is appropriately laminated, and the pressure is applied at 1 to 10 MPa at 170 to 300 ° C. for 10 minutes to 10 minutes. A method of thermocompression bonding for 3 hours may be mentioned.

5. Flexible Wiring Board As a method for producing a flexible wiring board from the above curable resin composition, there is a method comprising the following three steps. The first step is a step of applying a curable resin composition containing an active ester, an epoxy resin, and an organic solvent to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater. In step 2, the electrically insulating film coated with the curable resin composition is heated at 60 to 170° C. for 1 to 15 minutes using a heater to volatilize the solvent from the electrically insulating film and cure. In the third step, the curable resin composition is B-staged to the electrically insulating film, using a heating roll or the like, a metal foil is applied to the adhesive. are thermally compressed (preferably at a compression pressure of 2 to 200 N/cm and a compression temperature of 40 to 200° C.). If sufficient adhesion performance is obtained by going through the above three steps, it may be finished here, but if complete adhesion performance is required, conditions of 100 to 200 ° C. for 1 to 24 hours are required. is preferably post-cured with. The thickness of the curable resin composition film after final curing is preferably in the range of 5 to 100 μm.

6. Build-up Board As a method for producing a build-up board from the curable resin composition, there is a method comprising the following three steps. The first step is a step of applying the above-mentioned curable resin composition appropriately blended with rubber, filler, etc. to a circuit board having a circuit formed thereon by using a spray coating method, a curtain coating method, or the like, and then curing the composition. In the second step, after that, after drilling a predetermined through-hole portion etc. as necessary, it is treated with a roughening agent, and the surface is washed with hot water to form unevenness, and a metal such as copper is formed. The third step is a step of sequentially repeating such operations as desired to alternately build up resin insulating layers and conductor layers of a predetermined circuit pattern. It should be noted that it is preferable to form the through-hole portion after forming the outermost resin insulating layer. The first step can also be carried out by laminating a build-up film that has been previously coated to a desired thickness and dried, in addition to the above solution coating method. In addition, the build-up board of the present invention is obtained by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to manufacture a build-up substrate by omitting the steps of forming a hardened surface and plating.

7. BUILD-UP FILM TECHNICAL FIELD The present invention relates to a build-up film containing the curable resin composition. As a method for producing the build-up film of the present invention, the curable resin composition is applied onto a support film to form a curable resin composition layer to form an adhesive film for a multilayer printed wiring board. A manufacturing method is mentioned.

When producing a build-up film from a curable resin composition, the film softens under the lamination temperature conditions (usually 70 to 140° C.) in the vacuum lamination method, and simultaneously with the lamination of the circuit board, via holes present in the circuit board Alternatively, it is essential to exhibit fluidity (resin flow) that enables resin filling in the through-holes, and it is preferable to blend the above components so as to exhibit such properties.

Here, the diameter of the through-hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to allow resin filling within this range. . When both sides of the circuit board are laminated, it is desirable to fill the through holes by about half.

Specifically, the method for producing the adhesive film described above comprises preparing the varnish-like curable resin composition, applying the varnish-like composition to the surface of the support film (Y), and further heating. Alternatively, it can be produced by drying the organic solvent by blowing hot air or the like to form the composition layer (X) composed of the curable resin composition.

The thickness of the composition layer (X) to be formed is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

In addition, the composition layer (X) in the present invention may be protected with a protective film to be described later. By protecting the surface of the resin composition layer with a protective film, it is possible to prevent the surface of the resin composition layer from being dusted or scratched.

The support film and protective film described above are polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; Paper patterns and metal foils such as copper foils and aluminum foils can be used. The support film and protective film may be subjected to release treatment in addition to mud treatment and corona treatment.

Although the thickness of the support film is not particularly limited, it is usually 10 to 150 μm, preferably 25 to 50 μm. Also, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is cured by heating, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling after curing, the support film is normally subjected to a release treatment in advance.

8. Multilayer Printed Wiring Board A multilayer printed wiring board can also be produced using the film obtained as described above. In the method for producing such a multilayer printed wiring board, for example, when the composition layer (X) is protected by a protective film, after peeling off these, the composition layer (X) is directly applied to the circuit board. It is laminated on one or both sides of, for example, by a vacuum lamination method. The method of lamination may be a batch type or a continuous roll type. Moreover, the adhesive film and the circuit board may be heated (preheated) if necessary before lamination.

The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140° C. and the pressure bonding pressure is preferably 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

9. Fiber Reinforced Composite Material As a method for producing a fiber reinforced composite material from the curable resin composition, each component constituting the curable resin composition is uniformly mixed to prepare a varnish, which is then made of reinforcing fibers. It can be produced by polymerizing after impregnating a reinforcing base material.

Specifically, the curing temperature at the time of carrying out such a polymerization reaction is preferably in the temperature range of 50 to 250°C. , preferably 120 to 200°C.

The reinforcing fibers may be twisted yarns, untwisted yarns, or non-twisted yarns, but untwisted yarns and non-twisted yarns are preferable because they achieve both moldability and mechanical strength of the fiber-reinforced plastic member. Furthermore, as for the form of the reinforcing fibers, those in which the fiber direction is aligned in one direction or a woven fabric can be used. The woven fabric can be freely selected from plain weave, satin weave, etc., depending on the site and application. Specifically, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, and the like, which are excellent in mechanical strength and durability, can be used, and two or more of these can be used in combination. Among these, carbon fiber is particularly preferable because the strength of the molded article is excellent, and various types of carbon fiber such as polyacrylonitrile, pitch, and rayon can be used. Among them, a polyacrylonitrile-based one is preferable because a high-strength carbon fiber can be easily obtained. Here, the amount of reinforcing fibers used when impregnating a reinforcing base material made of reinforcing fibers with varnish to form a fiber-reinforced composite material is such that the volume content of the reinforcing fibers in the fiber-reinforced composite material is 40 to 85%. A range of amounts is preferred.

10. Fiber-reinforced resin molded product As a method for producing a fiber-reinforced resin molded product from the curable resin composition, a hand lay-up method or a spray-up method in which a fiber aggregate is laid in a mold and the above-mentioned varnish is laminated in multiple layers. Using either a mold or a female mold, the base material made of reinforcing fibers is impregnated with varnish and stacked to form a shape. Vacuum bag method for molding, SMC press method for compressing and molding a sheet of varnish containing reinforcing fibers in advance with a mold, RTM method for injecting the above varnish into a mating mold in which fibers are spread, etc. A method of manufacturing a prepreg by impregnating fibers with the above varnish and baking the same in a large autoclave can be used. The fiber-reinforced resin molded article obtained above is a molded article having reinforcing fibers and a cured product of the curable resin composition. Specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded article is , preferably in the range of 40 to 70% by mass, and particularly preferably in the range of 50 to 70% by mass in terms of strength.

11. Others Although the method for producing a semiconductor encapsulating material or the like has been described above, other cured products can also be produced from the curable resin composition. Other methods for producing the cured product can be produced by complying with a general curing method for a curable resin composition. For example, the heating temperature conditions may be appropriately selected according to the type of curing agent to be combined, the application, and the like.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The softening point of the active ester obtained below, the GPC chart, and the curable composition containing the active ester The heat resistance (glass transition temperature), dielectric properties (dielectric constant, dielectric loss tangent), and elastic modulus of the resulting cured product were measured and evaluated under the following conditions.

<Softening point of active ester>
The softening point (°C) of the active ester obtained below was measured according to JIS K7234 (ring and ball method).

<GPC measurement>
Measurement was carried out using the following measurement apparatus and measurement conditions, and GPC charts of active esters obtained in Synthesis Examples, Examples, etc. shown below were obtained. From the results of the GPC chart, it was confirmed that the target product (active ester) was produced from the reduction and disappearance of the raw material peak.
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation
Column: guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + Tosoh Corporation Made by "TSK-GEL G4000HXL"
Detector: RI (differential refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of solid content of the active ester obtained in the following Examples and the like was filtered through a microfilter (50 μl) and used.

[Example 1]
Synthesis of active ester (A-1) 220 g (2.0 mol) of catechol, 144 g (1.0 mol) of α-naphthol and toluene were placed in a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube and stirrer. 2061 g was charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Then, 505 g (2.5 mol) of isophthaloyl chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Thereafter, 1.0 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 1030 g of a 20% by mass sodium hydroxide aqueous solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under heating and reduced pressure to obtain 652 g of active ester (A-1) represented by the following structural formula.
This active ester (A-1) had an ester group equivalent weight of 137 g/equivalent, a softening point of 118° C., and a theoretical average number of repeating units n of 4 based on the raw material charge ratio.
The repeating unit number n is preferably 1 to 10, more preferably 2 to 8, still more preferably 3 to 5. When the number of repeating units n is within the above range, high heat resistance, low dielectric constant, and low dielectric loss tangent are obtained, which is preferable.

[Example 2]
Synthesis of Active Ester (A-2) The active ester ( A-2) was obtained in an amount of 759 g.
This active ester (A-2) had an ester group equivalent weight of 160 g/equivalent, a softening point of 128° C., and a theoretical average number of repeating units n of 4 based on the raw material charge ratio.

[Example 3]
Synthesis of active ester (A-3) 220 g (2.0 mol) of catechol of Example 1 was added to 332 g (2.0 mol) of tertiary-butyl catechol, and 144 g (1.0 mol) of α-naphthol was added to para-tertiary-butylphenol. 765 g of active ester (A-3) was obtained in the same manner as in Example 1, except that the content was changed to 150 g (1.0 mol).
This active ester (A-3) had an ester group equivalent weight of 161 g/equivalent, a softening point of 124° C., and a theoretical average number of repeating units n of 4 based on the raw material charge ratio.

[Comparative Example 1]
Synthesis of active ester (A-4) A flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer was charged with a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/equivalent, softening point 85° C.), 72 g (0.5 mol) of α-naphthol, and 630 g of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Then, 152 g (0.75 mol) of isophthaloyl chloride was charged, and the inside of the system was replaced with nitrogen under reduced pressure and dissolved. Thereafter, 0.6 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60° C. or less, and 315 g of a 20 mass % aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After completion of the reaction, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under heat and reduced pressure to synthesize an active ester (A-4).
This active ester (A-4) had an ester group equivalent weight of 223 g/equivalent and a softening point of 150°C.

[Examples 4 to 6 and Comparative Example 2]
As the epoxy resin, bisphenol A type epoxy resin ("850-S" manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent), the above active esters (A-1) to (A-4) as the curing agent, and the curing catalyst A curable composition was obtained by using N,N-dimethyl-4-aminopyridine (DMAP) and blending the composition shown in Table 1 below.
Each curable composition thus obtained was poured into molds of 11 cm×9 cm×2.4 mm and 11 cm×9 cm×1.6 mm, molded by a press at a temperature of 180° C. for 20 minutes, and then molded from the molds. The product was taken out and then cured at 175° C. for 5 hours to obtain an evaluation sample (cured product).

<Heat resistance (glass transition temperature)>
The resulting cured product with a thickness of 2.4 mm was cut into a size of 5 mm in width and 54 mm in length. Tension method: frequency 1 Hz, temperature increase rate 3 ° C./min), the temperature at which the ratio of elastic modulus change to viscoelastic modulus change is maximized (tan δ is the largest) is taken as the glass transition temperature (Tg) (° C.) , to evaluate the heat resistance.

<Dielectric properties (dielectric constant, dielectric loss tangent)>
The obtained cured product with a thickness of 1.6 mm was cut into a size of 2 mm in width and 10 mm in length. After drying in vacuum, the dielectric constant and dielectric loss tangent at 1 GHz of the test piece which was stored in a room at 23° C. and 50% humidity for 24 hours were measured.

<Elastic modulus>
The obtained cured product with a thickness of 2.4 mm was cut into a size of 10 mm in width and 80 mm in length. A flexural modulus was determined. In addition, it measured by n= 3 and used the average value. The film thickness and width of the test piece were measured at 5 points, and the average value was used for the calculated value.

From the evaluation results in Table 1 above, it was confirmed that by using the desired active esters in Examples 4 to 6, high heat resistance, low dielectric properties (especially low dielectric loss tangent), and high elastic modulus were achieved. did it. On the other hand, in Comparative Example 2, since the desired active ester was not used, it was confirmed that all evaluations were inferior to those of Examples.

1 is a GPC chart of active ester (A-1) obtained in Example 1. FIG. 1 is a GPC chart of active ester (A-2) obtained in Example 2. FIG. 1 is a GPC chart of active ester (A-3) obtained in Example 3. FIG.

Claims (9)

An aromatic compound (a) having two hydroxyl groups at adjacent positions on an aromatic ring, an aromatic monohydroxy compound (b), and an aromatic compound having two or more carboxyl groups and/or an acid halide or An active ester obtained by reacting an esterified product (c). The active ester according to claim 1, wherein the aromatic compound (a) is at least one compound selected from the group consisting of the following general formulas (1) to (3).

(In the above formula, each R independently represents a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 4, and m represents an integer of 0 to 2.) A curable resin composition comprising the active ester according to claim 1 or 2 and an epoxy resin. A cured product obtained by subjecting the curable resin composition according to claim 3 to a curing reaction. A prepreg comprising a reinforcing base material and a semi-cured product of the curable resin composition according to claim 3 impregnated in the reinforcing base material. A circuit board obtained by laminating the prepreg according to claim 5 and a copper foil, followed by thermocompression molding. A build-up film comprising the curable resin composition according to claim 3 . A semiconductor sealing material comprising the curable resin composition according to claim 3 . A semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material according to claim 8 .

Images