TWI516519B - Phenolic oligomer and method for producing the same - Google Patents

Description

Phenolic oligomer and preparation method thereof

The present invention relates to an epoxy resin for use in various types of adhesives, composites, coating materials, laminates, molding materials, and the like, and can be used as an epoxy novolac resin. A preferred phenolic oligomer which is a raw material, and particularly a hardener of an epoxy resin which can be used as a semiconductor sealing material or an underfill material, and a method for producing the same.

In the past, in the field of electronic materials, particularly semiconductor sealing, in terms of productivity and cost, resin sealing is the mainstream, and workability, formability, electrical properties, moisture resistance, mechanical properties, etc. Excellent, so the current situation is mainly the use of epoxy resin composition. In recent years, the demand for electrical and electronic equipment is becoming lighter, shorter, and more multifunctional. Therefore, the integration of semiconductors in a printed circuit board (PCB) is significantly accelerated, and the conventional pins are used. The DIP (Dual In-line Package) is transformed into a surface mount method (BGA, SOP, SiP, CSP). Furthermore, the use of a flip chip package as an effective mounting technique for high-density packaging has begun. Used in such a sealing material or underfill material, in terms of viscosity or heat resistance (glass transition temperature), a liquid epoxy resin using bisphenol A or F type, and an acid anhydride type or an amine type The resin composition of the hardener is the mainstream.

However, when an acid anhydride-based hardener is used, the hardened sealant may occur under the conditions of hot water, for example, under the conditions of a pressure cooker test. Hydrolysis, the resulting acid can corrode metal substrates or lines such as copper or aluminum, and has a problem of reduced wet durability. Further, when an amine-based curing agent is used, since it has strong activity, there is a problem that the reaction cannot be easily controlled.

On the other hand, in the conventional phenol-based curing agent, a semi-solid or solid phenol novolac resin is used in a solvent. Further, as the liquid phenol novolak resin, an allyl group-containing phenol novolak resin (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3), and a trihydroxyphenylmethane type phenol novolac are disclosed. An allylate of a varnish resin (for example, refer to Patent Document 4).

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-075866

Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-143774

Patent Document 3: Japanese Patent No. 3794349

Patent Document 4: Japanese Laid-Open Patent Publication No. 2-91113

However, the phenol novolac resin is inferior in fluidity when used in a sealing material. When a solvent is used to improve the fluidity, the solvent remaining in the sealing material after curing may become a void or the like, which may adversely affect reliability, which is not preferable. Further, the allyl-containing phenol novolak resin has a problem that fluidity is good (due to liquid form), but the heat resistance of the cured product is insufficient. Further, the fluidity of the trishydroxyphenylmethane type phenol novolak resin is not necessarily sufficient. Thus, the conventional phenol novolak resin, There is a problem that the low viscosity and the heat resistance of the cured product cannot be considered.

An object of the present invention is to provide a phenol-based oligomer which has high heat resistance to low-viscosity and a cured product thereof, a method for producing the same, a curing agent containing the phenol-based oligomer, and an epoxy resin and an epoxy resin. A resin composition, a sealing material for a semiconductor containing the epoxy resin composition, an underfill material, and the like.

The present invention has the following structure.

[1] A phenolic oligomer which is represented by the following formula (1);

(wherein n is an integer from 0 to 15, R is an allyl group, a1 and a3 are independently 0, 1, 2 or 3, and each a2 is independently 0, 1 or 2, and each R' is respectively Independently, it is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, but at least one of a1, each a2, and a3 is 2).

[2] A method for producing a phenol-based oligomer, comprising the step of: forming a phenol compound component containing at least one of a divalent allyl-substituted phenol compound represented by the following formula (2):

(wherein R is an allyl group, a is 1, 2 or 3), and at least one of the aldehyde compounds represented by the following formula (3): R'CHO (3)

(wherein, R' is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group).

[3] The production method according to the above [2], wherein the phenol compound component further contains at least one monovalent phenol compound represented by the following formula (4);

(wherein R is an allyl group and b is 0, 1, 2 or 3).

[4] The production method according to the above [2] or [3] wherein the molar ratio of the phenol compound component to the aldehyde compound is from 1.2:1 to 10:1.

[5] The production method according to any one of [2] to [4] wherein the phenol compound component contains allyl-substituted resorcinol.

[6] The production method according to any one of [2] to [5] wherein the phenol compound component contains 2,4-diallyl resorcinol and 4,6-diene. Propyl resorcinol is used as a main component.

[7] The production method according to the above [6], wherein the ratio of 4,6-diallylresorcin in the phenol compound component is from 15 mol% to 75 mol%.

[8] The production method according to any one of [2] to [7] wherein the reaction is carried out without a catalyst or in the presence of an acid catalyst.

[9] The production method according to any one of the above [2] to [8] wherein the phenol compound component is obtained by etherifying a hydroxy allylic acid of a divalent phenol, followed by rearrangement by kelson ( Claisen rearrangement) The allyl-substituted phenol nucleus is used to produce a divalent allyl-substituted phenol.

[10] A phenolic oligomer produced by the production method according to any one of [2] to [9] above.

[11] The phenolic oligomer according to the above [1] or [10], which has a rotational viscosity of from 0.01 to 150 Pa at 25 ° C with an E-type viscosity meter. s.

[12] A curing agent for an epoxy resin, which comprises the phenol oligomer according to the above [1], [10] or [11].

[13] An epoxy resin obtained by the reaction of the phenolic oligomer described in the above [1], [10] or [11] with epihalohydrin.

[14] An epoxy resin composition according to the above [1], [10] or [11], wherein the epoxy resin according to the above [13].

[15] An epoxy resin composition comprising a phenol resin and the epoxy resin according to [13] above.

[16] An epoxy resin composition comprising the above [1], [10] or [11] The phenol oligomer and the epoxy resin.

[17] A cured epoxy resin obtained by curing the epoxy resin composition according to any one of [14] to [16] above.

[18] A sealing material for a semiconductor element, which comprises the epoxy resin composition according to any one of [14] to [16] above.

[19] An underfill material for a semiconductor device, comprising the epoxy resin composition according to any one of the above [14] to [16].

[20] A semiconductor device which is sealed by using the sealing material according to [18] or the underfill according to [19] above.

According to the present invention, it is possible to provide a phenol-based oligomer which has high heat resistance to low-viscosity and a cured product thereof, a method for producing the same, a curing agent containing the phenol-based oligomer, and an epoxy resin and epoxy resin using the same. A resin composition, a semiconductor sealing material and an underfill material containing the epoxy resin composition, and the like.

[Phenol oligomer]

The phenolic oligomer of the present invention is represented by the following formula (1);

Where n is an integer from 0 to 15, R is an allyl group, a1 and a3 are each independently 0, 1, 2 or 3, and each a2 is independently 0, 1 or 2, and each R' is independently a hydrogen atom and a carbon number of 1 to 10. An alkyl group or an aryl group, wherein at least one of a1, each a2, and a3 is 2. Preferably, a1, each of a2, and a3 is 2 or more.

The phenolic oligomer represented by the above formula (1) is characterized by containing 0, 1, 2 or 3, preferably 1, 2 or 3, more preferably 1 or 2, still more preferably a condensation unit of a divalent phenol compound (hereinafter, also referred to as a divalent allyl-substituted phenol compound) substituted with two allyl groups and an aldehyde compound; and a conventional 1, 1, or 3 allyl-substituted 1 The phenolic compound of the phenolic compound and the formaldehyde compound (for example, Patent Documents 1 to 4) can achieve low viscosity and enhance the cured product (here, the cured product refers to the phenolic oligomer of the present invention as hardening). The heat resistance of the obtained cured material or the like of the epoxy resin (hereinafter, the phenolic oligomer is also used to improve the heat resistance of the obtained cured product) is referred to as heat resistance.

From the viewpoint of heat resistance, among all the structural units derived from the divalent phenol compound, the divalent phenol compound derived from two allyl groups present in the phenol oligomer represented by the above formula (1) The structural unit (a1, a2, and a3 are 2), preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and still more preferably 95 to 100 mol%.

From the viewpoint of the heat resistance, the range of the heat resistance of the cured product produced by the composition is not excessively increased by the viscosity of the phenolic oligomer, and the range represented by the above formula (1) is contained. In the phenol oligomer, the structural unit (a1, a2, and a3 of the allyl unsubstituted divalent phenol compound) may be used.

The degree of polycondensation n is preferably from 0 to 10, more preferably from 0 to 7, more preferably from the viewpoint of not excessively increasing the viscosity of the phenolic oligomer to cause a decrease in fluidity of the epoxy resin composition. Good is 0 to 5.

The method for producing a phenol-based oligomer of the present invention may, for example, be a method in which a phenol compound component containing a divalent allyl-substituted phenol compound is subjected to a polycondensation reaction with an aldehyde compound; or a divalent phenol and an aldehyde are used. After the compound is subjected to a polycondensation reaction, at least two allylic substituents are bonded to the above-mentioned structural unit derived from the phenol compound.

When the phenol-based oligomer of the present invention is used as a sealing material for a semiconductor and an underfill material, it is preferred to contain a divalent allyl-substituted phenol compound from the viewpoint of coating a phenol-based oligomer. A method of performing a polycondensation reaction with a phenol compound component and an aldehyde compound. In the case where the phenol-based oligomer is low-viscosity, it is preferred to produce a viscous-controlled phenol-based oligomer by the method for producing a phenol-based oligomer of the present invention to be described later.

[Method for Producing Phenol Oligomer]

The method for producing a phenol-based oligomer of the present invention (hereinafter also referred to as a production method of the present invention) comprises the step of containing at least one kind of divalent allylic acid represented by the following formula (2) a step of reacting a phenol compound component of a phenol compound with at least one aldehyde compound represented by the following formula (3);

(wherein R is an allyl group and a is 1, 2, or 3)

R’CHO (3)

(wherein R' is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group).

In the production method of the present invention, the phenol compound component preferably further contains at least one monovalent phenol compound represented by the following formula (4);

(wherein R is an allyl group and b is 1, 2, or 3).

In the production method of the present invention, the viewpoint of the heat resistance and the viscosity of the obtained phenol-based oligomer is within a predetermined range (hereinafter, the viewpoint of ensuring the viscosity of the phenol-based oligomer in a predetermined range is also referred to as a low-viscosity viewpoint. The ratio of the divalent allyl-substituted phenol compound represented by the formula (2) to the total amount of the phenol compound component (at least one of the divalent allyl groups represented by the formula (2)) The amount of the substituted phenol compound, or the amount of the divalent allyl-substituted phenol compound represented by the formula (2) and at least one monovalent phenol represented by the formula (4) when present Combination of the amount of compound Preferably, it is 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol%, further more preferably 95 to 100 mol%.

In the production method of the present invention, the phenol compound component other than the divalent allyl-substituted phenol compound represented by the formula (2) is preferably a heat-resistant property, a low viscosity, and a production efficiency. The ratio of the monovalent phenol compound represented by the above formula (4) to the total amount of the phenol compound component is preferably from 0 to 50 mol%, more preferably from 0 to 40 mol%, still more preferably 0 to 30 mol%, more preferably 0 to 20 mol%, still more preferably 0 to 10 mol%, still more preferably 0 to 5 mol%.

In the production method of the present invention, when the amount of the aldehyde compound added to the total amount of the phenol compound component is reduced, the obtained phenol oligomer is reduced in molecular weight, and as a result, the viscosity of the phenol oligomer can be reduced. Therefore, in the production method of the present invention, from the viewpoint of low viscosity, and from the viewpoint of ensuring the glass transition point and mechanical strength of the cured epoxy resin obtained by reacting the appropriate phenolic oligomer with the epoxy resin, , such that the total amount of the phenol compound component and the molar ratio of the aldehyde compound are from 1.2:1 to 10:1, preferably from 1.3:1 to 9:1, more preferably from 1.4:1 to 8:1. These raw material compounds are added.

The divalent allyl-substituted phenol compound represented by the formula (2) used in the production method of the present invention or the monovalent phenol compound represented by the formula (4) can be obtained by phenolic hydroxyallyl of phenol Etherification followed by rearrangement of the allyl substituted phenol core by Clayson. Raw material phenol can be used for benzene rings A monocyclic phenol having one or two phenolic hydroxyl groups. For example, examples of the monovalent phenol include phenol, cresol, ethylphenol, propyl phenol, butanol, xylenol, and butyl cresol; and as the divalent phenol, resorcin is exemplified. , catechol, hydroquinone, etc. From the viewpoint of ensuring heat resistance of the phenol-based oligomer of the present invention, preferred materials among these are divalent phenolic benzenediol and catechol, and more preferably resorcin.

The allyl etherification reaction can be carried out by a known method. For example, by dissolving a phenol of a raw material in an organic solvent and/or water, a base is added to form a phenolate, and an allyl halide such as allyl chloride, bromopropene or iodopropene is added thereto. It is carried out by reacting at room temperature to 100 ° C for 1 to 10 hours.

The organic solvent to be used herein may, for example, be an alcohol such as n-propanol or n-butanol; a ketone such as acetone or methyl ethyl ketone; or N,N-dimethylformamide or dimethylene? <JavaScript: show_detail (%221451403%22)> and other aprotic polar solvents. Although the yield of the allyl etherification reaction product varies depending on the solvent to be used, when the above organic solvent is used, the allyl etherification is usually carried out at a reaction rate of 70% or more. Since the solvent can be changed depending on the phenol reaction rate of the object, it can be used as long as it is a solvent in which the phenol of the raw material and the allyl etherified product are soluble. Further, the base may, for example, be a hydroxide of an alkali metal such as potassium hydroxide or sodium hydroxide. The amount used is equal to or more than the equivalent of the phenolic hydroxyl group to be etherified. The amount of the allyl halide to be added is equal to or higher than the equivalent of the base.

Next, the obtained allyl etherification reaction product is heated to about 150 to 250 ° C, and the allyl group bonded to the hydroxyl group is rearranged by the rearrangement of the kelson. A phenol nucleus, and an allyl substituted phenol compound can be obtained. The allyl group is usually rearranged to the ortho position to the hydroxy group, but is rearranged to the para position when the ortho position is filled with a substituent such as an alkyl group.

The phenol compound component containing at least one divalent allyl-substituted phenol compound represented by the formula (2) used in the production method of the present invention may be a compound obtained by reacting a divalent phenol of a raw material, as described above. It may also be a mixture of two or more compounds alone or in combination. The monovalent phenol compound represented by the formula (4) which can be used as the phenol compound in the production method of the present invention may be a compound obtained by reacting the monovalent phenol of the raw material as described above, or may be either alone or in combination. a mixture of the above. Specifically, examples of the monovalent allyl-substituted phenol compound include allylphenol, diallylphenol, and triallylphenol. Examples of the divalent allyl-substituted phenol compound include allyl-substituted catechols such as monoallyl catechol and diallyl catechol; monoallyl hydroquinone and diallylhydroquinone; Allyl-substituted hydroquinone such as triallyl hydroquinone; allyl-substituted resorcinol such as monoallyl resorcinol, diallyl resorcinol or triallyl resorcinol. From the viewpoint of low viscosity and heat resistance, preferred is allyl resorcinol, specifically, monoallyl resorcin, diallyl resorcin, and triene The resorcinol is preferably diallyl resorcinol. Further, a trivalent allyl-substituted phenol compound (monoallyl gallaphenol, diallyl gallapol, etc.) may be used insofar as the effects of the present invention are not impaired.

For example, if the hydroxyallyl etherification of resorcinol is carried out and the Crayson rearrangement is carried out, 2,4-diallyl resorcinol and 4,6-diene propene can be obtained. Divalent allyl group containing two isomers of resorcinol as a main component A mixture of substituted phenolic compounds (may also contain mono- or triallyl substituents of minor components, etc.). In this case, a mixture of divalent allyl-substituted phenol compounds containing two kinds of isomers as a main component may be used alone, but the isomers may be used as a main component. The mixture is also unaffected. From the viewpoint of productivity, it is preferred to use a mixture mainly composed of an isomer as a main component. Here, "the two kinds of isomers as a main component" means that the total amount of the two isomers is 50 to 100 mol% with respect to the total amount of the divalent allyl-substituted phenol compound. Preferably, it is 60 to 100% by mole, more preferably 70 to 100% by mole, still more preferably 80 to 100% by mole, particularly preferably 90 to 100% by mole, still more preferably 95 to 100% by mole. . Further, from the viewpoint of making the phenolic oligomer of the present invention low in viscosity, when the phenol compound component used is 2,4-diallyl resorcin and 4,6-diene When the two isomers of resorcin are used as the main component, the proportion of 4,6-diallyl resorcinol is preferably small. The proportion of 4,6-diallylresorcinol in the phenol compound component is preferably from 5 to 85 mol%, more preferably from 10 to 80 mol%, still more preferably from 15 to 75 mol%. %.

In the aldehyde compound used in the production method of the present invention, R _{3 is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, from the viewpoint of heat resistance and low viscosity. That is, a more preferred aldehyde compound is formaldehyde. Specific examples of the formaldehyde include, for example, a formalin aqueous solution, p-formaldehyde, and polyoxymethylene; examples of the alkyl aldehyde include hexanal and octanal; and examples of the aromatic aldehyde compound include benzaldehyde and o-hydroxybenzaldehyde. Salicyl aldehyde), p-hydroxybenzaldehyde and allyl phenyl formaldehyde. These aldehyde compounds may be contained alone or in combination. The aldehyde compound is preferably a fumarin aqueous solution which is easy to handle from the viewpoint of ease of handling and low viscosity, and a commercially available 42% formaldehyde aqueous solution can be used as it is.

In the production method of the present invention, the polycondensation reaction can be carried out without adding a catalyst or adding a catalyst. The acid catalyst used for the reaction is not particularly limited, and known ones such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid can be used. These may be used alone or in combination of two or more. When an acid catalyst is used, it is preferable to use oxalic acid or hydrochloric acid from the viewpoint of easy removal.

In the production method of the present invention, the amount of the acid catalyst used is preferably from 0.001 to 5.0 parts by weight, based on 100 parts by weight of the phenol compound component, from the viewpoint of ensuring an appropriate reaction rate for controlling the reaction. It is preferably 0.001 to 2.5 parts by weight, still more preferably 0.001 to 2.0 parts by weight.

In the production method of the present invention, the reaction temperature is preferably from 50 to 160 ° C and more preferably from 70 to 150 ° C from the viewpoint of allowing the aldehyde compound to react smoothly to ensure an appropriate reaction rate for controlling the reaction. The reaction time varies depending on the reaction temperature and the kind and amount of the catalyst to be used, but it is preferably from 1 to 24 hours, more preferably from 1 to 20 hours, still more preferably from 1 to 16 hours. The reaction pressure is usually normal pressure, but it is not affected by pressurization to a reduced pressure.

In the production method of the present invention, the unreacted allyl-substituted phenol compound may not be removed, but the method of removal is generally carried out under reduced pressure or under heating while blowing an inert gas. A method in which a phenolic compound is distilled to be excluded from the system. Further, in addition to thermal decomposition or reduced pressure removal, the acid catalyst may be removed by a washing method such as water washing.

From the viewpoint of heat resistance, obtained by the production method of the present invention The purity of the phenol-based oligomer is preferably 100% by weight. However, in consideration of the production efficiency, an unreacted product or a trace amount of a by-product may be contained in a range that does not impair the heat resistance effect of the present invention. The purity of the obtained phenolic oligomer composition is preferably from 70 to 100% by weight, more preferably from 80 to 100% by weight, still more preferably from 90 to 100% by weight, still more preferably from 95 to 100% by weight. %. Further, the measurement of the purity can be calculated by the measurement of GPC described later.

The phenol-based oligomer represented by the formula (1) of the present invention and the phenol-based oligomer obtained by the production method of the present invention are obtained by an E-type viscosity meter at 70 ° C from the viewpoint of low viscosity. The rotational viscosity is 0.01 to 100 Pa. s, preferably 0.01 to 50 Pa. s, more preferably 0.01 to 40 Pa. s, more preferably 0.01 to 30 Pa. s, and even more preferably 0.01 to 20 Pa. s, further preferably from 0.01 to 10 Pa. s, and further preferably from 0.01 to 5 Pa. s, and further preferably further 0.01 to 3 Pa. s.

The phenol-based oligomer represented by the formula (1) of the present invention and the phenol-based oligomer obtained by the production method of the present invention are further obtained by an E-type viscosity meter at 25 ° C from the viewpoint of low viscosity. The rotational viscosity is 0.01 to 150 Pa. s, preferably 0.01 to 130 Pa. s, more preferably 0.01 to 100 Pa. s, more preferably 0.01 to 80 Pa. s, more preferably 0.01 to 70 Pa. s, and more preferably from 0.01 to 60 Pa. s.

When the phenol-based oligomer represented by the formula (1) of the present invention is produced by the production method of the present invention, the rotational viscosity of the phenol-based oligomer obtained by the E-type viscosity meter is within the above range. In view of the above, it is preferred that the polycondensation degree n of the phenol-based oligomer is from 0 to 15, preferably from 0 to 10, more preferably 0. Further, it is preferably from 0 to 4, and the polycondensation reaction is controlled so that the average degree of polymerization of the phenol-based oligomer becomes 0 to 5, preferably 0 to 4, more preferably 0 to 3. Preferably. Specifically, the molar ratio of the phenol compound component (particularly a divalent allyl-substituted phenol compound) to formaldehyde is from 1.2:1 to 10:1, preferably from 1.3:1 to 9:1. Preferably, the polycondensation degree and the average polycondensation are controlled in the above preferred range by adding from 1.4:1 to 8:1.

The above-mentioned degree of polymerization and the average degree of polymerization can be determined by measurement of GPC as described later.

[Epoxy resin and epoxy resin composition]

The phenol-based oligomer represented by the formula (1) of the present invention and the phenol-based oligomer obtained by the production method of the present invention (hereinafter, these are collectively referred to as "the phenol-based oligomer of the present invention") It can also be used directly as a curing agent for epoxy resins in applications such as adhesives, coating materials, laminated materials, and molding materials.

The phenolic oligomer of the present invention can be produced into an epoxy resin (i) by reacting with an epihalohydrin.

When the phenolic oligomer of the present invention is reacted with an epihalohydrin to form an epoxy resin (i), for example, when epichlorohydrin is used as the epihalohydrin, the following method can be mentioned: The phenolic oligomer of the present invention is added with an excess of epichlorohydrin in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at 50 to 150 ° C, preferably 60 to 120 ° C. A method of allowing it to react for about 1 to 10 hours. In this case, relative to the phenolic oligomer of the present invention The hydroxyl equivalent weight, epichlorohydrin is used in an amount of 2 to 15 moles, preferably 2 to 10 moles. Further, the alkali metal hydroxide to be used is used in an amount of from 0.8 to 1.2 mol, preferably from 0.9 to 1.1 mol, based on the hydroxyl equivalent of the phenol oligomer of the present invention. After the reaction, the reaction is completed, and after the completion of the reaction, the excess epichlorohydrin is distilled off, and the residue is dissolved in an organic solvent such as methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the organic solvent is removed. Distillation, whereby an epoxy resin of interest can be obtained.

As the epihalohydrin to be reacted with the phenol oligomer of the present invention, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin or the like can be used. It is preferable to use epichlorohydrin in that it is industrially easy to obtain and has good reactivity with the hydroxyl group of the phenol-based oligomer of the present invention.

The epoxy resin composition (I) can be obtained by mixing the phenol-based oligomer of the present invention and the epoxy resin (i). A hardening accelerator or other additives may be added to the epoxy resin composition (I).

The epoxy resin composition (II) can be obtained by mixing the epoxy resin (i) with a phenol resin. A hardening accelerator or other additives may be added to the epoxy resin composition (II).

Since the phenol resin used in the epoxy resin composition (II) has a low viscosity of the epoxy resin (i), it is preferably a phenol novolac lacquer from the viewpoint of lowering the viscosity of the epoxy resin composition. Resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol novolac resin, such as cashew novolac resin, allyl phenol novolac resin; more preferably exemplified Such as phenol novolac resin, cresol novolac a lacquer resin, a phenol aralkyl resin, a biphenyl aralkyl resin, an allyl phenol novolak resin; more preferably, for example, a phenol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, an allylic acid Phenolic novolac resin.

The epoxy resin composition (III) can be obtained by mixing a phenol-based oligomer and an epoxy resin (ii). Examples of the epoxy resin (ii) include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a cresol novolak epoxy resin, a phenol novolac epoxy resin, and a trisphenol methane epoxy resin. A glycidyl ether type epoxy resin such as a resin or a biphenyl type epoxy resin, a glycidyl ester type epoxy resin, or a glycidylamine type epoxy resin halogenated epoxy resin is equivalent to an epoxy having two or more epoxy groups in one molecule. Resin. These epoxy resins are used alone or in combination of two or more. From the viewpoint of making the epoxy resin composition low in viscosity, a preferred epoxy resin is, for example, a bisphenol A type epoxy resin which is preferably in a liquid state at 70 ° C, more preferably at 25 ° C; A bisphenol F type epoxy resin which is in a liquid state at 70 ° C, more preferably 25 ° C, is preferred. A hardening accelerator or other additives may be added to the epoxy resin composition (III).

A curing accelerator which can be added to the epoxy resin compositions (I) to (III) (hereinafter, referred to as "the epoxy resin composition of the present invention") can be used to make an epoxy resin. A well-known hardening accelerator that reacts and hardens with a phenol resin. The hardening accelerator may, for example, be an organic phosphine compound, a boron salt thereof, a tertiary amine, a quaternary ammonium salt, an imidazole or a tetraphenylboron salt thereof. From the viewpoint of curability and low viscosity, It is preferably 2-ethyl-4-methylimidazole which is in a liquid state at 25 °C.

In the epoxy resin composition of the present invention, an inorganic filler may also be added as needed. Filling materials, mold release agents, colorants, coupling agents, flame retardants, etc. In particular, when used for semiconductor sealing applications, it is necessary to add an inorganic filler. Examples of such an inorganic filler include amorphous oxidized alumina, crystalline cerium oxide, aluminum oxide, calcium citrate, calcium carbonate, talc, mica, barium sulfate, etc., and are oxidized by amorphous. Antimony, crystalline cerium oxide, etc. are particularly preferred. Further, the ratio of the additives may be the same as the ratio of the known epoxy resin composition for semiconductor sealing.

The semiconductor sealing material includes a sealing material that seals the gap between the semiconductor element and the circuit board and the periphery of the semiconductor element, or an underfill material that seals only the gap between the semiconductor element and the circuit board. The sealing material may be in the form of a liquid, a paste, or a tablet.

The epoxy resin composition of the present invention can be obtained, for example, by reacting at 100 to 350 ° C to harden it to obtain a cured epoxy resin. Further, a semiconductor device obtained by sealing a semiconductor using the epoxy resin composition described above can be obtained by flowing an underfill material containing the epoxy resin composition into a gap between the semiconductor and the circuit substrate, and A method of curing an epoxy resin composition; or a method of flowing a sealing material containing the epoxy resin composition into a gap between the semiconductor and the circuit substrate and the periphery of the semiconductor to cure the epoxy resin composition. In the present invention, the sealing of the semiconductor element includes a step of flowing the underfill material into the gap between the semiconductor and the circuit substrate, and a step of hardening the underfill material, or including: injecting the sealing material into the gap between the semiconductor and the circuit substrate; The step of surrounding the semiconductor and the step of hardening the sealing material.

Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the invention is not limited to the embodiments. Also, "parts" herein means parts by weight.

(Example) [Synthesis Example 1] [Synthesis of allyl-substituted resorcinol]

In a glass 4-necked flask equipped with a thermometer, a charge/distillation port, a cooler, and a stirrer, 100.0 parts (2.4 mol) of sodium hydroxide and 600 ml of N,N-dimethylformamide were placed in advance. N,N-dimethylformamide 500 ml was dissolved and 110.1 parts (1.0 mol) of dihydroxybenzene was added dropwise. Thereafter, 191.3 parts (2.4 mol) of propylene chloride and 300 ml of N,N-dimethylformamide were added dropwise, and the mixture was reacted at 30 ° C for 6 hours. After neutralizing with hydrochloric acid and washing with water several times, the solvent was removed and distilled at 150 ° C to obtain 255.0 parts of allyletherified resorcinol.

255.0 parts of the obtained allyl etherified resorcinol was subjected to a rearrangement of Crayson at 190 ° C for 3 hours to obtain an allyl-substituted resorcinol (divalent allyl-substituted phenol compound) 250.0 of a yellow-brown liquid. Share. According to HPLC analysis (refer to the analysis method of <allyl-substituted phenol compound> (1) below), the obtained allyl-substituted resorcinol has a purity of 93%, 4,6-diallyl substituted The ratio is 48% (% is based on peak area).

[Synthesis Example 2] [Synthesis of allyl-substituted resorcinol]

In a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 196.0 parts (4.8 mol) of sodium hydroxide and 1200 ml of N,N-dimethylformamide were placed in advance. N,N-dimethylformamide 1000 ml of dissolved hydroquinone 220.2 parts (2.0 mol) was added dropwise. Thereafter, 382.7 parts (4.8 mol) of propylene chloride and 600 ml of N,N-dimethylformamide were added dropwise, and reacted at 30 ° C for 6 hours. The mixture was neutralized with hydrochloric acid and washed with water several times, and then subjected to solvent removal and distillation purification under reduced pressure at 150 ° C to obtain 490.0 parts of allyletherified resorcinol.

490.0 parts of the obtained allyletherified resorcinol was subjected to Clenson rearrangement at 190 ° C for 4 hours. 300 parts of the obtained allyl-substituted resorcinol was subjected to distillation purification using a Vigreaux tube at 160 ° C and a vacuum of 5 mmHg. After about 30 parts of the initial distillation was removed, 70.0 parts of an allyl-substituted resorcinol (a divalent allyl-substituted phenol compound) was obtained.

According to HPLC analysis (same as in Synthesis Example 1), the allyl-substituted resorcinol was a transparent liquid having a purity of 90%, and the ratio of the 4,6-diallyl substituent was 29%.

[Synthesis Example 3] [Synthesis of allyl-substituted resorcinol]

The residue obtained by distillation purification of Synthesis Example 2 was further purified by distillation at 165 ° C and a vacuum of 5 mmHg to obtain 110.0 parts of allyl-substituted resorcin.

According to HPLC analysis (same as in Synthesis Example 1), the allyl-substituted resorcinol was a clear liquid having a purity of 89%, and the ratio of the 4,6-diallyl substituent was 43%.

[Synthesis Example 4] [Synthesis of allyl-substituted resorcinol]

Further, the residue of the distillation purification of Synthesis Example 3 was at 175 ° C, The vacuum was purified by distillation at 3 mmHg to obtain 60.0 parts of allyl-substituted resorcinol (divalent allyl-substituted phenol compound).

According to HPLC analysis (same as in Synthesis Example 1), the allyl-substituted resorcinol was a clear liquid having a purity of 88%, and the ratio of the 4,6-diallyl substituent was 65%.

[Synthesis Example 5] [Synthesis of allyl-substituted resorcinol]

In a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 49.0 parts (1.2 mol) of sodium hydroxide and 300 ml of N,N-dimethylformamide were placed in advance. N,N-dimethylformamide 250 ml dissolved 55.1 parts (0.5 mol) of hydroquinone was added dropwise. Thereafter, 95.7 parts (1.2 mol) of propylene chloride and 150 ml of N,N-dimethylformamide were added dropwise, and the mixture was reacted at 30 ° C for 6 hours. After neutralizing with hydrochloric acid and washing with water several times, the mixture was decompressed at 150 ° C to carry out solvent removal and distillation to obtain an allyletherified resorcinol.

125.0 parts of the obtained allyletherified resorcinol was subjected to a rearrangement of 4.5% at 185 ° C for 4.5 hours. The obtained allyl-substituted resorcinol was subjected to distillation purification at 160 ° C and a vacuum of 4 mmHg using a thorn type fractionating tube. After about 20 parts of the initial distillation was removed, 50.0 parts of an allyl-substituted resorcinol (a divalent allyl-substituted phenol compound) was obtained.

According to HPLC analysis (same as in Synthesis Example 1), the allyl-substituted resorcinol was a transparent liquid having a purity of 97%, and the ratio of the 4,6-diallyl substituent was 23%.

[Synthesis Example 6] [Synthesis of allyl substituted catechol]

In a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 375.2 parts (2.7 mol) of potassium carbonate, 100.9 parts of catechol (0.9 mol), and acetone 1000 ml were placed, and then added dropwise. 280.8 parts (2.3 moles) of propylene bromide and 260 ml of acetone were reacted at 60 ° C for 13 hours. Thereafter, 500 ml of acetone was added thereto for filtration, concentration, and washing with water several times, followed by depressurization at 80 ° C to obtain an allyletherified catechol.

40.0 parts of diglyme and 2.0 parts of zinc chloride were added to 100.0 parts of the allyl etherified catechol obtained above, and the residue was rearranged at 160 ° C for 7 hours, and then purified by distillation. 75.4 parts of allyl-substituted catechol (divalent allyl-substituted phenol compound) was obtained.

According to HPLC analysis (same as in Synthesis Example 1), the obtained allyl-substituted catechol was a colorless transparent liquid having a purity of 87%.

[Example 1] [Synthesis of phenolic oligomers]

To a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 28.5 parts (0.15 mol) of allyl-substituted resorcinol obtained in Synthesis Example 1 and 5.4 parts of 42% fumarin were added. 0.08 mol) and reacted at 100 ° C for 8 hours. 63.0 parts of pure water of 90 ° C or more was charged, and after washing with water, the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to the gel permeation chromatography analysis (refer to the following <Analysis method of phenolic oligomer and cured product> (7)), the purity of the obtained phenolic oligomer is 96.2% by weight, and the degree of polymerization (n) From 0 to 4, the average degree of polymerization is 0.8. Moreover, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.54 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 89Pa. s (refer to the same (1)).

[Embodiment 2] [Synthesis of phenolic oligomers]

57.0 parts (0.30 mol) of allyl-substituted resorcinol obtained in Synthesis Example 1 and 10.7 parts of 42% of fumarin were added to a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer. 0.15 moles, and 0.6 parts of oxalic acid as an acidic catalyst was added, and reacted at 100 ° C for 4 hours. After charging 125.0 parts of pure water of 90 ° C or more, and washing with water, the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 98.5% by weight, a degree of polymerization (n) of 0 to 4, and an average degree of polymerization of 0.6. Moreover, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.55 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 91Pa. s (same as in the first embodiment).

[Example 3] [Synthesis of phenolic oligomers]

To a four-necked glass flask equipped with a thermometer, a charge/distillation port, a cooler, and a stirrer, 57.0 parts (0.30 mol) of allyl-substituted resorcinol obtained in Synthesis Example 1 and 5.4 parts of 42% fumarin were added. 0.08 moles, 0.6 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 4 hours. 125.0 parts of pure water of 90 ° C or more was poured, and after washing with water, the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained The phenol oligomer had a purity of 69.7% by weight, a degree of polymerization (n) of 0 to 4, and an average degree of polymerization of 0.5. Further, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.05 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 1.6Pa. s (same as in the first embodiment).

[Example 4] [Synthesis of phenolic oligomers]

To a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 16.7 parts (0.08 mol) of allyl-substituted resorcinol obtained in Synthesis Example 1 and 4.2 parts of 42% fumarine were added ( 0.05 moles, 0.2 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 1 hour. After 50.0 parts of pure water of 90 ° C or more was added, after washing with water, the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 98.3% by weight, a degree of polymerization (n) of 0 to 4, and an average degree of polymerization of 0.7. Moreover, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.65 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 124Pa. s (same as in the first embodiment).

[Example 5] [Synthesis of phenolic oligomers]

To a four-necked glass flask equipped with a thermometer, a charge/distillation port, a cooler, and a stirrer, 380.0 parts (2.00 mol) of allyl-substituted catechol obtained in Synthesis Example 6 and 7.1 parts of 42% fumarine (0.1) were added. Mohr), 7.6 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 24 hours. 500.0 parts of pure water of 90 ° C or more is charged, and after washing with water, the temperature is raised to 180 ° C and carried out. Dehydration, the unreacted components are removed by a reduced pressure-vapor treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 95.7 wt%, a degree of polycondensation (n) of 0 to 6, and an average degree of polymerization degree of 1.2. Moreover, it is a liquid at 70 ° C and a viscous solid at 25 ° C. The rotational viscosity at 70 ° C is 14.3 Pa. s, the rotational viscosity at 25 ° C is 107Pa. s or more (same as in the first embodiment).

[Embodiment 6] [Synthesis of phenolic oligomers]

57.0 parts (0.30 moles) of allyl-substituted resorcinol obtained in Synthesis Example 3 and 10.7 parts of 42% humamine were added to a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer. 0.15 moles, 0.6 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 4 hours. After charging 125.0 parts of pure water of 90 ° C or more, and washing with water, the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 97.9% by weight, a degree of polymerization (n) of 0 to 4, and an average degree of polymerization of 0.6. Further, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.32 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 32Pa. s (same as in the first embodiment).

[Embodiment 7] [Synthesis of phenolic oligomers]

57.0 parts (0.30 moles) of allyl-substituted resorcinol obtained in Synthesis Example 2 and 10.7 parts of 42% of fumarin were added to a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer. 0.15 mol), as acid 0.6 parts of oxalic acid of the sexual medium was reacted at 100 ° C for 4 hours. After charging 125.0 parts of pure water of 90 ° C or more, and washing with water, the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 98.5% by weight, a degree of polymerization (n) of 0 to 4, and an average degree of polymerization of 0.5. Further, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.28 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 26Pa. s (same as in the first embodiment).

[Embodiment 8] [Synthesis of phenolic oligomers]

4 parts of allyl-substituted resorcinol obtained in Synthesis Example 4 (0.24 mol) and 8.6 parts of 42% fumarin were added to a glass 4-necked flask equipped with a thermometer, a charge/distillation port, a cooler, and a stirrer. 0.12 moles, 0.5 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 4 hours. After 100.0 parts of pure water of 90 ° C or more was poured, the water was washed, and the temperature was raised to 120 ° C, and water and unreacted components were removed by a reduced pressure treatment.

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 98.2% by weight, a degree of polymerization n ₁ of 0 to 4, and an average degree of polymerization n ₂ of 0.6 at 70 ° C. And 25 ° C for liquid, 70 ° C rotation viscosity of 0.51Pa. The rotational viscosity of s and 25 ° C is 72 Pa. s.

[Embodiment 9] [Synthesis of phenolic oligomers]

The allyl-substituted resorcinol obtained in Synthesis Example 5 was added to a four-necked glass flask equipped with a thermometer, a charge/distillation port, a cooler, and a stirrer. A portion (0.22 mol), 7.9 parts (0.21 mol) of 42% fumarine, 0.4 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 4 hours. After 100.0 parts of pure water of 90 ° C or more was put in, and it wash-washed, it heated up to 120 degreeC, and the water and the un

According to gel permeation chromatography analysis (same as in Example 1), the obtained phenol-based oligomer had a purity of 98.2% by weight, a degree of polymerization (n) of 0 to 4, and an average degree of polymerization of 0.5. Moreover, it is a liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.25 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 25Pa. s (same as in the first embodiment).

[Comparative Example 1]

In a glass 4-necked flask equipped with a thermometer, a charge/distillation port, a cooler, and a stirrer, 670 parts (5.0 moles) of o-allylphenol and 71.4 parts (1.0 moles) of 42% of formalin were added as an acid touch. The medium was 6.7 parts of oxalic acid and reacted at 100 ° C for 5 hours. 500 parts of pure water of 90 ° C or more was charged and washed with water. Thereafter, the temperature was raised to 165 ° C and dehydrated, and the unreacted components were removed by a reduced pressure treatment. The obtained phenolic oligomer is liquid at 70 ° C and 25 ° C, and has a rotational viscosity of 0.07 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 1.7Pa. s (same as in the first embodiment).

[Comparative Example 2]

According to the embodiment of Patent Document 4 cited in the prior art document, a polyolefin compound (g (hydroxyallylphenyl) methane type phenol novolak resin) is synthesized.

<Synthesis of phenol (hydroxyallylphenyl)methane type phenol novolak resin>

For glass with thermometer, charge/distillation, cooler and mixer A 4-neck flask was charged with 400 parts of phenol (4.26 mol), 47.2 parts of o-hydroxybenzaldehyde (0.38 mol), and 1.0 part of p-toluenesulfonic acid, and the reaction was carried out at 130 ° C under a nitrogen stream, and cooled to 95 ° C. . After neutralizing with a 25% aqueous sodium hydroxide solution, 400.0 parts of pure water at 90 ° C or higher was charged and washed with water. Thereafter, the internal temperature was raised to 150 ° C, and the unreacted components were removed by a reduced pressure-vapor treatment. The obtained resin is solid at 70 ° C and 25 ° C, and has a melt viscosity of 0.9 Pa at 150 ° C. s.

<Allylation synthesis of phenol (hydroxyallylphenyl)methane type phenol novolak resin>

In a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 100.0 parts of the phenol (hydroxyallylphenyl)methane type phenol novolak resin produced above, and 2-propanol 250.0 were placed. After dissolving until homogeneous, 40.7 parts of sodium hydroxide (1.02 mol) was added and stirring was continued for 1 hour. After 79.6 parts of propylene chloride (1.02 mol) was added dropwise thereto over 10 minutes, the reaction was carried out at 75 ° C for 5 hours to etherify the allyl group. After the 2-propanol was removed, 400.0 parts of pure water at 90 ° C or higher was charged to wash the by-produced salt. The temperature was raised to 190 ° C for dehydration, and the Clarison was rearranged for 6 hours. The obtained resin is liquid at 70 ° C, semi-solid at 25 ° C, and has a rotational viscosity of 1.1 Pa at 70 ° C. s, the rotational viscosity at 25 ° C is 107Pa. s or more (same as in the first embodiment).

[Comparative Example 3] <Synthesis of cresol novolac resin>

In a glass 4-necked flask equipped with a thermometer, a charge/distillation port, a cooler and a stirrer, 660 parts (6.00 m) of cresol and 42% of formalin were added. 42.4 parts (0.60 mol), 0.2 parts of oxalic acid as an acidic catalyst, and reacted at 100 ° C for 5 hours. 500.0 parts of pure water of 90 ° C or more was charged, and after washing with water, the temperature was raised to 170 ° C and dehydrated, and the unreacted components were removed by a reduced pressure-vapor treatment. The obtained cresol novolak resin is solid and has a melt viscosity of 0.07 Pa at 150 ° C. s.

<Allylation Synthesis of Cresol Novolak Resin]

In a glass 4-necked flask equipped with a thermometer, a charging/distillation port, a cooler, and a stirrer, 50.0 parts of the above-produced cresol and 100.0 parts of 2-propanol were placed, dissolved in a uniform state, and 36.5 parts of sodium hydroxide was added thereto. (0.91 mol), stirring was continued for 1 hour. After 75.0 parts of propylene chloride (0.96 mol) was added dropwise thereto over 10 minutes, the reaction was carried out at 60 ° C for 5 hours to etherify the allyl group. After the 2-propanol was removed, 500.0 parts of pure water at 90 ° C or higher was charged to wash the by-produced salt. The temperature was raised to 190 ° C for dehydration, and the Clarison was rearranged for 6 hours. The obtained resin is solid at 70 ° C and 25 ° C, and the melt viscosity at 150 ° C is 10 Pa. s above.

<Analysis method of allyl substituted phenol compound>

(1) HPLC

High-performance liquid chromatography was performed under the following conditions to determine the purity of the allyl-substituted phenol compound and the 2,4- allyl substitution and 4,6 The proportion of the isomer of the allyl substituent.

. Column: ODS-80Ts 250×4.6mm

. Detection method: visible light detector (UV 254nm)

. Mobile phase: acetonitrile / water = 60 / 40

. Flow rate: 1.0ml/min

. Column temperature: 40 ° C

. Sample adjustment: 0.2g of sample solution was taken, diluted with 40g of acetonitrile, and injected into 20μL

An example of the measurement result of PHLC in Fig. 1 is an example of Synthesis Example 5. Each peak is shown in the figure: a retention time of about 5.4 corresponds to a 2,4-diallyl substitution, and a retention time of about 5.9 corresponds to a 4,6-diallyl substituent as a relative peak area. The ratio of the total of the above two kinds of peak areas was calculated to be 96% of the purity of the allyl-substituted phenol compound.

Further, the ratio of the 2,4-diallyl substituent calculated by dividing each peak area by the purity was 77%, and the ratio of the 4,6-diallyl substituent was 23%.

(2) Identification of allyl substituted isomers

The allyl-substituted phenol compound (allyl-substituted resorcin) was separated by thin layer chromatography (TLC; thin-layer chromatography) under the following conditions to obtain two kinds of samples.

TLC separation conditions

. TLC 1mm (Silica gel 60 F254 PLC Plates)

. Developing solvent: hexane/ethyl acetate = 2/1

Next, the two samples were analyzed by GC and ¹ H NMR to identify the isomer of the allyl-substituted resorcinol.

GC analysis conditions

. Column: G-100 1.2mm I.D×40m, film thickness 1.0μm

. Column temperature / temperature rise conditions: start at 100 ° C, rise at 4 ° C / min Warm to 200 ° C for 15 minutes

. Injection / detection temperature: 250 ° C

. Gas pressure: He=100kPa, Air=50kPa, H ₂ =65kPa

. Sample adjustment: After filtering the reaction solution through a filter, inject 0.1 μL

Examples of GC analysis results are shown in Fig. 2 and Fig. 3.

In the sample 1 of Fig. 2, the ally-substituted resorcinol having a peak ratio of about 17 minutes was maintained at about 17 minutes, but the sample 2 of Fig. 3 was 21% of ally for about 17 minutes. The base-substituted resorcinol was 79% allyl-substituted resorcinol at 19 minutes.

Further, the results of ¹ H NMR analysis are shown in Figs. 4 and 5 .

In the sample 1 of Fig. 4, each peak has one peak, and the sample 2 in Fig. 5 has two peaks each, and the respective integral ratios are approximately the same ratio as the GC analysis result of 21:79.

<Analysis method of phenolic oligomer and cured product>

(1) Rotational viscosity

. The E-type viscometer uses the TVH type manufactured by Toki Sangyo Co., Ltd.

. About 1.2 ml of the sample (the phenolic oligomer obtained in Examples 1 to 9) was placed in a cup attached to an E-type viscometer, and the cup was set to a thermostat set at a temperature of 25 ° C or 50 ° C. Liquid device (F25-MP manufactured by Julabo).

. The measurement of the rotational viscosity of the above sample was started with an E-type viscometer, and the value of the rotational viscosity was read as the value of the rotational viscosity of the stable point.

(2) OH equivalent

(Summary: acetonitrile with ethyl acetate, the excess chlorinated hydrazine is decomposed by water and titrated with alkali)

. Weighing scale sample (phenolic oligomer obtained in Examples 1 to 9) 1 g, adding 1,4-two 10 ml of the alkane was dissolved.

. After confirming dissolution, 10 ml of a 1.5 mol/L chlorinated acetonitrile/anhydrous toluene solution was added, and the mixture was cooled to 0 °C.

. 2 ml of pyridine was introduced and reacted in a water bath of 60 ± 1 ° C for 1 hour.

. After the reaction, the mixture was cooled and added with 25 ml of pure water, and the mixture was uniformly mixed, whereby the acetyl chloride was decomposed.

. 25 ml of acetone and phenolphthalein were added.

. A 1 mol/L sodium hydroxide aqueous solution was used for titration until the sample solution was colored reddish purple.

. The blank operation (blank) (no sample) was carried out as described above and simultaneously measured.

The following formula is calculated and obtained.

OH equivalent [g/eq.] = (1000 × W) / (f × (B-A))

Here, f, B, and A are as follows.

W: sample weight [g]

f: factor of 1 mol/L potassium hydroxide aqueous solution (factor <javascript:void(0);>)=1.002

B: The amount of 1 mol/L potassium hydroxide aqueous solution required for the determination of the blank sample [ml]

A: The amount of 1 mol/L potassium hydroxide aqueous solution required for the measurement of the sample [ml]

(3) Water absorption rate

. In the mold, the sample (with the composition shown in Table 3 and Table 4) The oxy-resin composition was cured at 150 ° C for 5 hours and 180 ° C for 8 hours to form a sample.

Dimensions; (Φ 50 ± 1) × (3 ± 0.2) (diameter × thickness; mm)

. The surface of the sample was carefully cleaned and the weight of the sample was measured.

. The sample was placed in a 100 ml sample vial and 80 ml of pure water was added.

. The water was allowed to absorb water for 24 hours in a hot air circulating dryer at 95 °C.

. Thereafter, it was taken out by a drier and immersed in a low temperature constant temperature bath to be cooled to 25 °C.

. After cooling, the moisture attached to the surface was carefully wiped off and the weight was measured.

. The water absorption rate was calculated by the following formula.

Water absorption rate [%] = ((B-A) / A) × 100

A: weight before water absorption [g]

B: weight after water absorption [g]

(4) Glass transition temperature (Tg)

. In the mold, a sample (an epoxy resin composition having the compositions shown in Tables 3 and 4) which was cured at 150 ° C for 5 hours and at 180 ° C for 8 hours was cut into the following dimensions to prepare a sample.

Dimensions; (50 ± 1) × (40 ± 1) × (100 ± 1) (length × width × height; mm)

. The measuring device was placed in TMA-60 (manufactured by SHIMADZU) and measured in an N ₂ atmosphere.

. The temperature increase rate was measured at 3 ° C /min to 350 ° C, and the temperature at the inflection point was determined as the glass transition temperature (Tg).

The glass transition temperature is the benchmark for heat resistance, and the higher the glass transition point, the higher the resistance. The more excellent the heat.

(5) Gel time (gel time)

. The sample (the epoxy resin composition having the composition shown in Tables 3 and 4) was placed in a test tube, immersed in an oil bath at 150 ° C, and the epoxy resin was stirred by a glass rod at intervals of 1 time every 1 second. Things. The time during which the above-mentioned stirring resistance became large was measured as the gelation time.

(6) Mechanical properties of the hardened material (elastic modulus/stress)

. In the mold, a sample (an epoxy resin composition having the compositions shown in Tables 3 and 4) which was cured at 150 ° C for 5 hours and at 180 ° C for 8 hours was cut into the following dimensions to prepare a sample.

. Dimensions; (75 ± 1) × (6 ± 1) × (4 ± 1) (length × width × height; mm)

. Measuring device; material testing machine (autograph) (type; AG-5000D SHIMADZU system)

The compression bending test was carried out at room temperature at a head speed of 2.0 mm/min and a distance between two points; 50 mm.

(7) GPC

Gel permeation chromatography (GPC) was carried out under the following conditions to determine the degree of polymerization (n) of the phenol-based oligomer and the average degree of polymerization of the phenol-based oligomer.

. Device: Gel Permeation Chromatograph (HLC-8020) made by Tosoh Corporation

. Pipe column: TSKgelG2000HXL 4, G3000HXL and G4000HXL each made by Tosoh Corporation are connected in series

. Lysate: tetrahydrofuran

. Dissolution flow: 1.0 mL / min

. Column temperature: 40 ° C

. Detection method: visible light detector (UV)

. Standard curve: Made with standard styrene

An example of the GPC test result shown in Fig. 6 is an example of the first embodiment. The peak values are shown in the figure: the hold time is about 50.5, the score is corresponding to n=0, the hold time is about 48.5, the score is corresponding to n=1, the hold time is about 47.0, the score is corresponding to n=2, and the hold time is about 46.1. n=3, holding time of about 45.3 is corresponding to n=4, and the total value of the total value of each peak area multiplied by the degree of polymerization (n) divided by the total area of the peak is 0.8.

Further, the total value of the respective peak areas of n = 0 to 4 divided by the total area of the peaks was 96.2%.

The purity of the divalent allyl-substituted phenol compound of the starting materials in Examples 1 to 9 and Comparative Examples 1 to 3, the ratio of the 4,6-diallyl substituted compound, the synthesis conditions of the allyl-substituted phenol compound, and The properties of the obtained phenolic oligomer are shown in Tables 1 to 2.

In Table 2, the E-type viscosity is solid and semi-solid, which means that the phenolic compound is not dissolved at 25 ° C or 70 ° C, so the viscosity cannot be measured.

The phenol-based oligomers obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were used as a curing agent, and an epoxy resin and a curing accelerator were added to prepare an epoxy resin composition. Epikote 828EL (bisphenol A type liquid epoxy resin, epoxy equivalent 186 g/eq) manufactured by Nippon Epoxy Resin Co., Ltd. was used as the epoxy resin, and the above-mentioned hardening accelerator was made using Shikoku Chemical Co., Ltd. 2E4MZ (2-ethyl-4-methylimidazole). The epoxy resin composition is prepared such that the epoxy group equivalent of the epoxy resin is the same as the hydroxyl equivalent of the phenol oligomer. The composition of the epoxy resin composition is shown in Tables 3 and 4.

Further, the epoxy resin composition was heated to 150 ° C, melt-mixed, and vacuum defoamed, and then poured into a mold heated to 150 ° C, and hardened at 150 ° C for 5 hours and 180 ° C for 8 hours to obtain a ring. Oxygen cured product. The physical properties of the obtained epoxy resin cured product are shown in Tables 3 and 4.

In Tables 3 and 4, α ₁ is a linear expansion coefficient at a temperature below the glass transition point (Tg), and α ₂ is a linear expansion coefficient at a temperature above the glass transition point (Tg).

As is apparent from the results of the above examples, each of the epoxy resin compositions produced in the examples was used as a sealing material or an underfill material for a semiconductor element.

Fig. 1 shows the results of HPLC measurement of the allyl-substituted resorcinol obtained in Synthesis Example 5.

Fig. 2 is a graph showing the results of GC analysis of a sample (sample 1) obtained by sampling TLC from an isomer mixture of allyl-substituted resorcin.

Fig. 3 is a view showing the results of GC analysis of a sample (sample 2) obtained by sampling TLC from an isomer mixture of allyl-substituted resorcin.

Fig. 4 shows the results of ¹ H NMR analysis of the above sample 1.

Fig. 5 shows the results of ¹ H NMR analysis of the above sample 2.

Fig. 6 is a GPC chart showing the phenol oligomer obtained in Example 1.

The phenol oligomers and their manufacturing methods are the only ones in this case. However, the drawings in this case are all graphs of experimental data, so it is not enough to represent the technical characteristics of this case.

Claims (20)

a phenolic oligomer which is represented by the following formula (1); (wherein n is an integer from 0 to 15, R is an allyl group, a1 and a3 are independently 0, 1, 2 or 3, and each a2 is independently 0, 1 or 2, and each R' is respectively Independently, it is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, but at least one of a1, each a2, and a3 is 2). A method for producing a phenol-based oligomer, comprising the step of: phenol compound component containing at least one of a divalent allyl-substituted phenol compound represented by the following formula (2): (wherein R is an allyl group, a is 1, 2 or 3), and at least one aldehyde compound represented by the following formula (3): R'CHO (3) (wherein R' is hydrogen The step of reacting an atom, an alkyl group having 1 to 10 carbon atoms or an aryl group. The production method according to the second aspect of the invention, wherein the phenol compound component further contains at least one monovalent phenol compound represented by the following formula (4); (wherein R is an allyl group and b is 0, 1, 2 or 3). The production method according to claim 2, wherein the molar ratio of the phenol compound component to the aldehyde compound is from 1.2:1 to 10:1. The production method according to claim 2, wherein the phenol compound component contains allyl-substituted resorcinol. The production method according to claim 2, wherein the phenol compound component contains 2,4-diallyl resorcinol and 4,6-diallyl resorcinol as a main component. . The production method according to claim 6, wherein the ratio of 4,6-diallylresorcin in the phenol compound component is from 15 mol% to 75 mol%. The production method according to claim 2, wherein the reaction is carried out in the absence of a catalyst or an acid catalyst. The production method according to claim 2 or 3, wherein the phenol compound component is obtained by etherifying a hydroxyallyl group of a divalent phenol, followed by an allyl group by Claisen rearrangement A divalent allyl-substituted phenol obtained by substituting a phenol nucleus. A phenolic oligomer produced by the production method according to any one of claims 2 to 9. The phenolic oligomer according to claim 1 or 10, which has a rotational viscosity of from 0.01 to 150 Pa‧s at 25 ° C in an E-type viscosity meter. A hardener for epoxy resins, which comprises the phenolic oligomer described in claim 1, 10 or 11. An epoxy resin obtained by the reaction of a phenolic oligomer described in claim 1, 10 or 11 with epihalohydrin. An epoxy resin composition comprising the phenolic oligomer described in claim 1, 10 or 11, and the epoxy resin according to claim 13 of the patent application. An epoxy resin composition comprising a phenol resin and an epoxy resin as described in claim 13 of the patent application. An epoxy resin composition comprising the phenolic oligomer described in claim 1, 10 or 11, and an epoxy resin. An epoxy resin cured product obtained by hardening an epoxy resin composition according to any one of claims 14 to 16. A sealing material for a semiconductor component, which is in the scope of claim 14 The epoxy resin composition according to any one of the items 16. An underfill material for a semiconductor device, which comprises the epoxy resin composition according to any one of claims 14 to 16. A semiconductor device which is sealed with a sealing material as described in claim 18 or an underfill as described in claim 19.