TW201113245A - Phenolic compound and manufacturing method thereof - Google Patents

Abstract

Provided is a phenolic compound exhibiting low viscosity and low hygroscopicity under 50 DEG C, and bringing out on excellent mechanical properties when cured by reacting with epoxy resin. The phenolic compound is obtained by reacting phenol (6), aromatic aldehyde (7) and formaldehyde, and condensedly polymerizing these compounds, in which the above mentioned reaction is progressed by either one of the methods for obtaining the phenolic compound described below: a method of reacting phenol (6), aromatic aldehyde (7) and formaldehyde in one step; a method of reacting the phenol (6) and aromatic aldehyde (7), and then reacting with formaldehyde; or a method that the reaction product of phenol (6) and aromatic aldehyde (7) is reacted with the reaction product of phenol (6) and formaldehyde, and relative to one mole formaldehyde, 0.1 to 4.0 moles aromatic aldehyde (7) is used, and the rotational viscosity obtained from the E type rotational viscosimeter of phenolic compound under 50 DEG C is adjusted to 0.01 to 100Pa.s.

Description

201113245 ar VI. Description of the invention: • [Technical field to which the invention belongs] _ 纟 月 有关 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为A phenol (phen 〇丨)-based compound which can be used as a raw material of an epoxidized secret varnish resin, in addition to a cured material or a molding material (a curing agent for an epoxy resin such as m〇lding). [Prior Art] In the field of electronic materials, especially semiconductor (1C) sealing, resin sealing is the mainstream in terms of productivity and cost, and it is excellent in workmanship, electrical properties, richness, and mechanical properties. For this reason, the epoxy resin composition is mainly used in the current situation. For such a hardener, it can be exemplified: phen〇i novolac resin, various amines, acid anhydrides, and especially semiconductors (1C) For the purpose of sealing, phenol novolac resin is mainly used from the viewpoints of heat resistance and reliability. In recent years, electronic devices have become more lightweight, shorter, more multifunctional, and semi-finished. The body (IC) is significantly accelerated, and the mounting method when the package is mounted on a printed circuit board (PCB) is gradually being inserted from the conventional pin (DIP ' dual in- 1 ine package, dual in-line package) is surface mount (BGA (bal 1 grid array 'ball array), SOP (small out-line package 'small package), SiP (single in-line package, single column) In-line package), CSP (chip~scale package). Furthermore, the fiip chip mounting method has been applied to the installation technology for efficient high-density mounting. Therefore, 322229 5 201113245 gradually becomes this. The sealing material or underfill material is used. These are made of a liquid epoxy resin and a liquid acid anhydride, a hardener such as an amine or a chelating amine, and as a benzene anti-clear varnish hardener, a semi-solid or solid benzoic acid varnish resin or It is used as a phenol phenolic acid varnish resin dissolved in a solvent. The sealing material using such a benzene-to-knee varnish resin is of course poor in fluidity, and the solvent is used because the solvent is contained in the hardened sealing material to adversely affect the performance. Although an acid anhydride is also tried to form a solventless sealant, since the hardened sealant is hydrolyzed in the presence of hot water, for example, a pressure cooker test, the generated acid is a metal substrate such as corrosion aluminum. Or the reason of the line, resulting in reduced humidity life. Further, since the amine and the guanamine group have a strong activity, they are not good in terms of reliability. Then, as the liquid phenol novolak resin, an allyl phenol phenol varnish resin (Patent Document 1) has been disclosed, but there is a problem that heat resistance is insufficient. Further, an allylate of a phenol novolak resin of a trihydroxyphenyldecane type (Patent Document 2) has been disclosed, but fluidity is not sufficient enough to have low viscosity and heat resistance of a cured product. problem. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2000-169537. For the above-mentioned phenolic phenolic phenol novolak resin (patent document 3), the phenolic 322229 6 201113245 • s 2 or more types are used together. The structure of the moon will change depending on the situation at the time of the reaction, and there is a problem of lack of reprQdueibility during production. [Explanation] [Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned conventional problems and to provide one that can be used. (A benzoate-based compound which exhibits good mechanical properties when it is hardened by reaction with an epoxy resin when it is low in viscosity and low in hygroscopicity. [Effect of the Invention] The phenolic compound of the present invention can be used at 5 (TC) The lower viscosity and low moisture absorption and good mechanical properties can be exhibited when reacting with an epoxy resin. That is, the phenol compound of the present invention can not reduce hygroscopicity and low expansion at high temperatures. Properties and low deformability (for the elasticity of bending, the displacement (diSpiacement) and strength at the time of breaking), the viscosity at 50 C is lowered and the heat resistance (glass transition point) is improved. [Means for solving the problem] In the invention, the result of the intensive study in order to achieve the above object is 'specifically, δ' has the following constitution. [1] A phenolic compound, which is a phenol represented by the general formula (6), and a general formula (7) The aromatic aldehyde compound is obtained by reacting with formaldehyde, and is a phenol system obtained by polycondensation of the phenol, the aromatic aldehyde compound, and/or the furfural. Compound, 7 322229 201113245 The above reaction is carried out by any one of the following methods: preparing the phenolic compound by the first-stage reaction of the benzene, the aromatic awake compound, and the citric acid described above. a method of reacting the phenol with the aromatic aldehyde compound and then reacting it with the formic acid to obtain the phenanthrene compound; or reacting the phenol with the aromatic aldehyde compound a reaction product of the reaction product and a reaction product obtained by reacting the phenol with the furfural to obtain the above-mentioned compound, and in the foregoing reaction, the molar number of the formaldehyde至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至lOOPa · s way to adjust

(wherein, f represents an integer of 0 to 3, and R7 represents any of a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and an allyl group which may have a substituent, If f is 2 or more, each R7 may be the same or different), 8 322229 201113245

(wherein b and c represent an integer of 0 to 3, and R8 may be the same or different, and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, may have a substituent When any of the allyl groups is 2 or more, each R8 may be the same or different h [2]-phenolic compound, and is a repeating unit represented by the following general formula (1) and the following The benzene compound having a repeating unit represented by the formula (2) as a main constituent unit, the number average molecular weight of the phenol compound is 4 〇〇 to 6 〇〇, and the phenol compound is obtained by an E type viscosity meter at 50 t: The rotational viscosity is from 0.01 to lOOPa. s

(wherein, a, b, and c each independently represent an integer of 〇 to 3, and R1 and R2 each independently have a carbon number of 1 to 4 of a substituent, or a straight-chain or a sub-independently represent a hydrogen atom, a dendritic group, and may have a substitution. Any one of the allyl groups, such as & or b is 2 or more, each R1 and each R2 may be the same or different) 322229 9 201113245

(wherein d represents an integer of 0 to 3', and R3 represents any of a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and an allyl group which may have a substituent. If d is 2 or more, it may be the same or different at R3. [3] A method for producing a phenol-based compound, wherein the phenol compound represented by the general formula (6-1) and the aromatic aldehyde compound represented by the general formula (7-1) are reacted with furfural. The phenol, the aromatic aldehyde compound, and/or the formic acid·polycondensation method, wherein the phenol compound is produced by reacting the phenol with the aromatic aldehyde compound in the presence of a basic catalyst, and then 0倍摩尔, and the system is used in the presence of the above-mentioned aldehydes in the presence of the above-mentioned aldehydes. 01至至〇〇Pa · s Adjusted by the viscosity of the above-mentioned benzene-based compound at 50 ° C from the E-type viscometer

(wherein ' ί - l denotes an integer from 〇 to 3, R 7-1 denotes a hydrogen atom, a direct bond or a branched alkyl group which may have a slave number of 10 322229 201113245, and a olefin having a substituent Any one of the propyl groups, if ί-l is 2 or more, each may be phase-same or different)

Wherein 'b-1, c-1 represents an integer of 0 to 3, and rh may be the same or different, and represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 丨 to 4 having a substituent, Any one of the allyl groups which may have a substituent, if b_i is 2 or more, each R8-1 may be the same or different. [4] An epoxy resin which is obtained by reacting the above-mentioned phenol-based compound with epihalohydrin. [5] An epoxy resin composition comprising the above-mentioned (IV), a compound and an epoxy resin. =-=Epoxy resin composition containing the desired resin (10) (10) and μ (4) (except for the phenol-based compound) (7) An epoxy resin cured product which is a resin. Founder. The epoxy resin composition is cured (8) - a sealing material of a semiconductor element or a material. ..., the epoxy resin composition [9] The bottom of the semiconductor element is filled with epoxy resin composition. It is sealed by the above-mentioned [10] - semiconductor, ^ month 'J bottom filling material. Use of other sealing materials or 322229 11 201113245 [Embodiment] Hereinafter, the contents of the present invention will be described in detail. The phenol-based compound (hereinafter, simply referred to as a phenol-based compound or a phenol-based compound of the present invention) of the present invention is a phenol represented by the general formula (6) (hereinafter, abbreviated as phenol in the present invention), and a general formula. (7) An aromatic aldehyde compound (hereinafter, abbreviated as an aromatic aldehyde compound in the present invention) and a phenol compound obtained by reacting with furfural (hereinafter, simply referred to as formaldehyde in the present invention). In other words, the first phenol compound of the present invention is a phenol compound obtained by polycondensation of the phenol of the present invention, the aromatic aldehyde compound of the present invention, and/or the furfural of the present invention after the above reaction. Further, the first phenol compound of the present invention is subjected to the above reaction by any of the following methods; the phenol of the present invention, the aromatic aldehyde compound of the present invention, and the furfural of the present invention are used. a method of producing a phenol-based compound by a one-stage reaction; a method of reacting the phenol of the present invention with the aromatic aldehyde compound of the present invention, and then reacting it with the above-mentioned furfural; or by reacting the phenol of the present invention with a reaction product obtained by reacting an aromatic aldehyde compound in the present invention, a reaction product obtained by reacting a phenol of the present invention with a furfural of the present invention, and, in the foregoing reaction, The aldehyde-based compound of the present invention is used in an amount of from 0.1 to 4.0 mol of the aromatic aldehyde compound of the present invention, and 12 322229 201113245 to give the benzoin compound of the present invention at 50 ° C. The viscosity is 〇. 〇ι to lOOPa. The way to adjust it.

OH

(wherein 'ί denotes an integer of 〇 to 3. R7 represents any of a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and an allyl group which may have a substituent. When f is 2 or more, each R7 may be the same or different. R'

(7) (wherein b, C represents an integer of 0 to 3, which is the same or different, and represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, may have a substitution When R3 of the base is used, each R8 may be the same as the same shirt). 4 乂 phenol-based compound of the present invention, main constituent unit: It is preferred to condense the benzene group derived from the benzene group derived from the present invention and the aromatic residue derived from the aromatic substance derived from the present invention by the following repeating unit. (Card densatiQn) derived from the repeating unit represented by the general formula (1); and the benzene residue derived from the present invention is condensed with the vine derived from the present invention, and is represented by the general formula (2) f complex unit, and, in general, the residue of the general formula (3) 322229 13 201113245 2 derived from the benzene-n-residue of the phenol derived from the present invention is constituted as both terminals. In this case, the ratio of the number of moles of the aromatic passage in the present invention to the number of moles in the present invention is often the same as the number of the fresh elements represented by the general formula (1) (four). (2) The ratio of the number of repeating units indicated is substantially the same.

(wherein, a, b, and c each independently represent an integer of 〇 to 3. Each of Ri and R2 independently represents a hydrogen atom, a straight bond or a branched thio group having a carbon number of 取代 to 4 which may have a substituent, and may have a substitution Any one of the radical propyl groups, if a or b is 2 or more, each R1 and each R2 may be the same or different.

(wherein d represents an integer represented by 〇 to 3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and an allyl group H which may have a substituent such as d is 2 In the above case, each r3 may be the same or different).

(3) 322229 14 201113245 m • (wherein 'e represents an integer of 〇 to 3. R4 represents a hydrogen atom, a straight or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, may have a substituent Any one of allyl groups. When e is 2 or more, each r4 may be the same or - not the same. Therefore, the description of the phenol of the present invention is also applicable to R3 &a in the repeating unit represented by the general formula (1), R3 and the heart and the general formula in the repeating unit represented by the general formula (2) ( 3) R4 and e in the repeating unit represented, and the description of R8, b&c of the aromatic aldehyde in the present invention is also applicable to R2, b and c in the repeating unit represented by the general formula (1). The description of the formaldehyde in the present invention also applies to the disk residue in the repeating unit represented by the general formula (2). The benzoquinone compound of the present invention may contain a compound which can react with the benzene of the present invention, the aromatic acid of the present invention, and/or the present invention, without departing from the effects of the present invention. Residues derived from other compounds that are capable of undergoing a polycondensation reaction. Such a repeating unit may, for example, be a residue derived from the following compounds: 4,4, bis(?oxymethyl)biphenyl, d__bis(chloromethyl)biphenyl, 1,4- Bis(methoxymethyl)benzene, u-bis(chloronaphthoquinone, f朌, benzene age. The less the amount of residues derived from other compounds mentioned above, the better, the benzene compound t of the present invention Preferably, it is 5 mol% or less, and more preferably 2 mol% or less, and then preferably less than i mol%, and particularly preferably does not contain such a residue. Further, it is preferably in such a manner as to be such a content. ',' When the benzene-aged compound of the present invention is produced, the benzene age of the present invention is adjusted: the aromatic compound of the present invention, the hydrazine of the present invention, and the amount of the other (4) 322229 15 201113245. The second phenol system of the present invention The compound is a phenol-based compound containing a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) as a main constituent unit, and the number average molecular weight thereof is contained in the first phenol-based compound of the present invention. The phenolic system of the present invention has a rotational viscosity of from 0.1 to 100 Pa · s at a temperature of from 50 to 600. In the method for producing a phenol compound, the aromatic acid compound represented by the general formula (6-1) and the aromatic acid compound represented by the general formula (7-1) are reacted with citric acid, and the general formula is (6-1) A phenol, an aromatic aldehyde compound represented by the general formula (7-1), and/or a furfural, which is obtained by a general formula (6-1) in the presence of a basic catalyst. a step of reacting a phenol with an aromatic aldehyde compound represented by the general formula (7-1), and then reacting with furfural in the presence of an acid catalyst, and in this step, relative to the aforementioned furfural The number of ears is from 0. 1 to 4.0 mol of the aromatic aldehyde compound, and the viscosity of the phenol compound represented by the general formula (6-1) at 50 ° C from an E-type viscometer. Adjusted for the way from 0.01 to lOOPa · s.

(wherein, f-Ι represents an integer of 0 to 3. R7-1 represents a hydrogen atom, may be 16 322229 201113245 has a substituent of a carbon number of 1 to 4 of a straight or branched alkyl group, a substituentable alkene Any of the propyl groups. If ί-l is 2 or more, each RH may be the same or different.

(wherein b-1 and c-1 represent an integer of 0 to 3. R8-1 may be the same or different, and represents a hydrogen atom, a linear or branched burning of a carbon number of 1 to 4 which may have a substituent. Any one of the allyl groups which may have a substituent. When b-1 is 2 or more, each R8_1 may be the same or different. The phenol-based compound of the present invention is produced by reacting the phenol of the present invention represented by the general formula (6) with the aromatic aldehyde compound of the present invention represented by the general formula (7), and then reacting it with the present invention. Further, the method for producing a phenol-based compound according to the present invention is equivalent to the phenol of the present invention represented by the general formula (6) and the aromatic compound of the present invention represented by the general formula (7). The aldehyde compound is reacted in the presence of a basic catalyst, and then reacted with furfural in the present invention in the presence of an acidic catalyst. Therefore, the aromatic aldehyde compound of the present invention represented by the general formula (7) and the method of reacting the furfural of the present invention, which are described in the general formula (6), which will be described later or later, are described. The detailed description also applies to the detailed description of the method for producing the phenolic compound of the present invention, and the description of R7 and f in the general formula (6) also applies to the description of ίΓ1 and f-1 17 322229 201113245, The description of R8, b and c in the formula (7) also applies to the descriptions of b, l and c-1. [The first phenol-based compound of the present invention and the production method of the present invention] The phenol of the present invention is a preferred residue derived from the phenol of the present invention as described in the general formula (6). As described in the general formulas (1), (2), and (3), the compound group as described below has a hydroxyl group on the benzene ring, and f (that is, a, d, and e) is When it is 2 or more, each of eight, that is, R1, R3 and R4) may be the same or different, and may represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and may have a substitution. Any of the radicals of the base. When the phenols of the present invention are used singly or in combination of two or more kinds, there is no problem. Specific examples of the phenol in the present invention include phenol, cresol, ethyl benzoquinone, propyl benzene, butyl benzene, xylene, butyl methyl benzene, allyl benzene, and C. Since the viscosity of the obtained benzene compound is low, it is particularly preferable that a, d, and 2 and R7 (that is, 'Rl, R3, R4, and R7-1) It is an allyl 2-allylphenol, that is, o-allylphenol. When phenpanene is mixed with o-mercaptopropylphenol as the phenol, since the reactivity of phenol is high, there is a tendency that the phenol has a reaction with the aldehyde compound earlier than the allyl phenol. Therefore, when the production of f (that is, a, d, e, and f_1) is 2 and R7 (that is, R1, R3 'R4, and R7-1) is an allyl benzene compound, it is preferably used. It is substantially free of phenolic o-olefins 18 322229 201113245 propyl benzene. In the phenpanic compound of the present invention, a compound derived from a methylene crosslinking group between the stupid and benzene residues in the present invention can be preferably used in the present invention. acid. Further, the form of the crucible (4) in the present invention is not particularly limited, and an aqueous solution of an aluminum plate, a paraformaldehyde, a trioxane or the like may be decomposed to form formaldehyde in the presence of an acid. The polymer. It is preferably an aqueous formaldehyde solution which is easy to handle, and a commercially available 42% aqueous formic acid solution can be used as it is. The aromatic aldehyde compound of the present invention which forms one of the crosslinked compounds derived from the phenol residue of the phenol of the present invention is derived from the aromatic form of the present invention as described in the general formula The residue of the aldehyde compound is preferably as described in the above formula (1), more preferably as described in the above general formula (4), and is preferably as in the above general formula (5). As described, it is an aromatic aldehyde compound group having 0 to 3 hydroxyl groups on a stupid ring, R8 and R2 representing a hydrogen atom, or a substituted or unsubstituted direct bond or fraction having 1 to 4 carbon atoms. The dendritic group, substituted or unsubstituted allyl group. The aromatic brewing compounds of the present invention are used alone or in combination of two or more kinds, and have no problem. The disc compound is preferably a benzaldehyde, a salicylaldehyde, a p-hydroxybenzaldehyde or an allyl strepaldehyde, and more preferably a ruthenium or a paraformaldehyde. 19 322229 201113245

(wherein, a represents an integer of 0 to 3. R1 represents any of a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and an allyl group which may have a substituent. When a is 2 or more, each R1 may be the same or different.

(wherein a represents an integer of 0 to 3. R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and any of the allyl groups which may have a substituted fluorene. When a is 2 or more, each R1 may be the same or different. The phenolic compound of the present invention can be obtained, for example, by the following production method. The method of obtaining the phenol-based compound of the present invention by the one-stage reaction of the phenol of the present invention, the aromatic aldehyde compound of the present invention, and the furfural of the present invention; A method for producing a phenol-based compound of the present invention; and a method for producing a benzene-based compound of the present invention by a three-stage reaction of 20 322229 201113245. The method for producing a phenol-based compound of the present invention by a two-stage reaction is exemplified by first reacting the phenol of the present invention with the aromatic aldehyde compound of the present invention, and then A method of reacting with the formaldehyde of the present invention; and a method of first reacting the phenol of the present invention with furfural of the present invention, and then reacting it with the aromatic aldehyde compound of the present invention. The method for producing the phenol compound of the present invention by the three-stage reaction may, for example, be a reaction product obtained by reacting the phenol of the present invention with the aromatic aldehyde compound of the present invention, and The three-stage reaction in which the reaction product obtained by the reaction of the phenol of the present invention with the formaldehyde of the present invention is reacted. In the above production method, the phenol system of the present invention is obtained by reacting the phenol of the present invention with the aromatic aldehyde of the present invention and then reacting it with the furfural of the present invention in a two-stage reaction. The method of the compound is preferred because the distribution of the number of repeating units represented by the general formula (1) or the distribution of the number of repeating units represented by the general formula (2) is narrow. When the phenol-based compound of the present invention is produced by the above two-stage reaction, it is also possible to add the hop of the present invention together with the aldehyde compound of the present invention added in the second stage. The phenol compound of the present invention is preferably a ratio of a repeating unit represented by the general formula (1) to a repeating unit represented by the general formula (2) (the number of repeating units of the general formula (1) / the repeating unit of the general formula (2) The average of the number is 0.1 to 4.0, as the number of repeating units represented by the general formula (1) / the repeating formula represented by the general formula (2) 21 322229 201113245 The number of repeating phenolic compounds is less than 0.1 The glass transition temperature of the epoxy resin composition obtained with the epoxy resin is lowered. On the other hand, when the number of repeating units represented by the general formula (1) / the number of repeating units represented by the general formula (2) exceeds 4.0, the viscosity of the phenolic compound and the epoxy resin composition rises, so that the flow Sexual deterioration. In particular, if the number of repeating units represented by the general formula (1) in the molecule is smaller than the number of repeating units represented by the general formula (2), that is, the number of repeating units represented by the general formula (1) / general formula ( 2) When the number of repeating units is less than 1.0, the viscosity of the obtained phenol compound at 50 ° C is preferably lowered. Therefore, when the phenol compound of the present invention reacts the phenol of the present invention, the aromatic aldehyde compound of the present invention, and the formaldehyde of the present invention, the present invention is used with respect to the molar number of formaldehyde in the present invention. 0倍摩尔。 0. 1 to 1. 0倍莫耳,优选为0. 1至1. 0倍摩尔. In particular, it is preferred to produce a phenol-based compound produced by a two-stage reaction as follows: a phenol of the present invention is reacted with an aromatic aldehyde compound of the present invention in advance in the presence of a basic catalyst, and the reaction is carried out. After the end, the acid is neutralized with an alkaline catalyst, and then, the formaldehyde in the present invention is added in the presence of an acid catalyst to carry out a reaction. When the reaction is carried out in such a two-stage reaction, in the preferred state obtained by the reaction, the distribution of the number of repeating units represented by the general formula (1) or the distribution of the number of repeating units represented by the general formula (2) is narrow. And the molecular weight is easily controlled, and as a result, the desired viscosity is easily obtained. 22 322229 201113245 In the anti-phenolic phenolic compound of the present invention and the aromatic aldehyde compound of the present invention, if an acid catalyst is used, the reaction will not proceed sufficiently, and the aromatic aldehyde will be unreacted. Residual situation. The aforementioned unreacted aromatic aldehyde, such as • can be removed by washing or distilling the reaction product. In the production of the phenolic compound of the present invention, the ratio of addition of all of the aldehydes in the present invention to the total of the aldehydes in the aromatic aldehyde compound of the present invention and the formaldehyde in the present invention is preferably relative to the present invention. The phenol of the invention is added in such a manner that all the discs are made of 0.01 to 〇4. When the amount of the benzene-based compound in the present invention is too small, the amount of the benzene-based compound is formed in a large amount, and when the benzene-based compound is reacted to obtain a cured epoxy resin, the ring is obtained. The glass transition point of the oxygen tree will decrease, or the mechanical strength will decrease. In addition, when the amount of addition of the whole secret class to the present invention is too large, the degree of benzoquinone compound is increased, and the handleability is deteriorated. The alkaline catalyst is not particularly preferable. There are two restrictions on the month of sodium, oxyhydroxide, and hydrazine. It can be used to remove organic and water from bicyclo[5,4,0] eleven -7, and U-diazepine. In the manner of use, it is particularly preferred that the method is relative to the aromatic precursor of the present invention: liquid. The amount of the alkaline catalyst used is 〇······················· It is preferable that when the amount of the basic catalyst used is too small, the amount of the aromatic compound which Hr c should remain may be insufficient, and the amount of the alkaline catalyst is not excessive. There will be problems, 322229 23 201113245 However, the use of the acid catalyst used for neutralization increases, and there is a tendency to take a long time in the removal step of the salt formed during neutralization. Further, in the case where an acid catalyst is used for the reaction in the first stage, the reaction rate is slow, and the unreacted aromatic aldehyde compound tends to remain. In the method for producing a phenol-based compound of the present invention, the acid catalyst used in the reaction with the neutralizing agent of the basic catalyst or furfural is not particularly limited, and hydrochloric acid, oxalic acid, sulfuric acid, or the like may be used. Phosphoric acid, p-toluenesulfonic acid and the like are well known. These acid catalysts may be used alone or in combination of two or more. From the viewpoint of easy removal, among the above, oxalic acid and hydrochloric acid are particularly preferred. 001至2. 5。 The 001 to 5.0. 001至0. 00至份。 0. 001至0. 0重量份,更优选为0. 001至1. 0重量份,更优选为0. 001至0. 5重量份,更优选为0. 001至0 The range of 1 part by weight is very suitable for use. For example, when the amount of the acid catalyst used is less than 0.001 part by weight, the reaction rate tends to be slow, and if it exceeds 1.0 part by weight, the reaction proceeds sharply. It is difficult to control the situation of the reaction. The reaction conditions in the present invention differ depending on the structure of the phenol used in the present invention and the ratio of the aromatic aldehyde compound in the present invention to the amount of furfural used in the present invention, but the present invention is first The reaction temperature between the phenol and the aromatic aldehyde compound in the present invention is preferably from 70 to 160 ° C, more preferably from 70 to 150 ° C, still more preferably from 90 to 150 ° C, still more preferably from 90 to 130 ° C. When the reaction temperature is less than 70 ° C, the reaction rate is 24 322229 201113245, and the unreacted aromatic compound tends to remain. When the reaction temperature exceeds 160 ° C, it is difficult to control the reaction, and it is difficult to stably obtain the phenol-based compound of the present invention. The reaction time varies depending on the reaction temperature or the kind and amount of the catalyst to be used, but it is preferably from 1 to 24 hours. Next, the reaction product of the phenol of the present invention with the aromatic aldehyde compound of the present invention (the reaction product may contain an unreacted raw material) and the reaction with the furfural of the present invention are preferably 50°. C to 120 ° C, particularly preferably 80 to 110 ° C. If the reaction temperature is less than 50 ° C, the reaction rate becomes slow, and unreacted furfural tends to remain. When the reaction temperature exceeds 120 °C, it is difficult to control the reaction, and it is difficult to stably obtain the phenol-based compound of the present invention. The reaction time varies depending on the reaction temperature or the kind and amount of the catalyst to be used, but it is preferably from 1 to 24 hours. The reaction pressure in the present invention is usually carried out under normal pressure, but there is no problem even if it is carried out under reduced pressure. The method for removing the unreacted phenol compound in the present invention is generally a method in which the phenol is distilled off to remove the phenol by heating under a reduced pressure or while blowing an inert gas. Further, the removal of the acid catalyst can be carried out by washing or the like in addition to thermal decomposition or pressure reduction. In the above reaction of the phenol of the present invention, the aromatic aldehyde compound of the present invention, and the furfural of the present invention, the phenol compound of the present invention is obtained from the viewpoint of ensuring a low viscosity at 50 ° C. The rotational viscosity of the phenolic compound of the present invention obtained by an E-type viscometer at 5 (using E type)

25 322229 S 201113245 Viscosity meter (manufactured by Toki Sangyo Co., Ltd.) The sample of the phenol-based compound of the present invention is measured at a sample temperature of 5 (rc) to obtain a rotational viscosity of 0.1 to 100 Pa.s, preferably 80 Pa. s or less, more preferably 7 〇pa: s or less, preferably 60 Pa·s or less, preferably 〇〇1 to 8 〇pa · s, more preferably o. oi to 70 Pa.s, more preferably 〇1 to 6〇Pa s, then preferably ^ to 5Pa· s' is better for 〇.1 to 2pa. s mode adjustment. The method of adjustment is as described above, which can be exemplified: And/or the present formic acid, more preferably benzoquinone, as the aromatic compound in the present invention, the molar number of the aromatic acid compound in the present invention is preferably adjusted to the molar number of the formic acid in the present invention. 0. 1 to 3 〇 Moer's more tuned to (U to 2.0 Moules, and then better adjusted to 〇41〇 Mo Er others, as is well known in the art, as commonly known in the art, for example The general formula „ „ indicates the distribution of the number of repetitions of the early number or the general formula (2) indicates that the distribution of the number of complex elements of the 4 is narrowed; or财 丨 全部 全部 全部 〇 〇 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 The number average molecular weight of the compound of the compound of the present invention is preferably _ to coffee, more preferably 450 观点, from the viewpoint that the rotational viscosity obtained by the £-type viscometer can be within the above preferred range. 01至100Pa · The rotational viscosity of the benzoin compound of the present invention is 0. 01 to 100 Pa. In the range of s, it will be in a liquid state at a temperature of 50 °c at a temperature of 50 °c (in detail, at a sample temperature of 5 (a state in which it is not crystallized under rc), the present invention will be used. The phenolic novolac resin which is a phenolic compound is excellent in fluidity when it is processed on a semiconductor element, and is suitable as a sealing material or an underfill material for a semiconductor element. [The second phenolic compound of the present invention] this invention The second phenol-based compound has the following repeating unit as a main constituent unit: '- a condensation of a phenol residue derived from the phenol derived from the present invention with an aromatic aldehyde residue derived from the aromatic aldehyde of the present invention a repeating unit represented by the general formula (1); and a repeating unit represented by the general formula (2) obtained by condensing a phenol residue derived from phenol of the present invention with formaldehyde derived from the present invention, and usually The residue represented by the general formula (3) derived from the phenol residue of the phenol in the present invention is composed of both terminals. Thus, the description of the phenol and the phenol of the present invention is also applicable to the general formula (1). R1 and a in the repeating unit represented by (4) and (5), the repeating unit MRid of the general formula (2), and R4 and e in the repeating unit represented by the general formula (3), and the aromatic in the above-described invention The descriptions of R8, b and c of the aldehyde are also applicable to R2, b and c in the repeating unit represented by the general formula (1), and the description of the above-mentioned formaldehyde in the present invention is also applicable to the repeating unit represented by the general formula (2). Formaldehyde residue. 27 322229 201113245 A preferred method for producing the second compound of the present invention is the same as the preferred method for producing the first benzene material or compound of the present invention. The phenol-based compound of the present invention can be reacted with the benzophenone of the present invention, the aromatic aryl group of the present invention and/or the hydrazine of the present invention, without departing from the effects of the present invention. A residue derived from an octane compound which is capable of undergoing a polycondensation reaction. For such a repeating unit, n enumerates residues derived from the following compounds: 4,4,-bis(methylmethyl)biphenyl, 4,4,-dichloromethyl), stupid, U-double (A) Oxymethyl) stupid, 1,4,-bis(chloroindenyl)naphthylbenzene. The above-mentioned residue derived from the residue of the other compound is more and more excellent. Among the compounds of the present invention, preferably, the A 5 mol% or less is more preferably 2 mol 〇 / ❶ or less, and more preferably Less than or equal to the ear, and preferably no such residue. Further, it is preferable to adjust the amount of the aromatic acid compound in the present invention, the aromatic acid compound in the present invention, the 曱_ and other compounds in the present invention in such a manner as to be such a content. In the second benzene material and the compound of the present invention, the number average molecular weight is preferably from 0 to 55 Å from the viewpoint of ensuring a low degree of aeronautical. Here, the number average molecular weight is illustrated in the example. From the viewpoint of ensuring a low point at 5 (TC), the second benzoate compound of the present invention is the rotation point of the second benzene (tetra) compound of the present invention obtained by the E-type viscometer in the fifth generation. (The use of a meter (manufactured by Toki Sangyo Co., Ltd.) to measure a sample of about 12 ml at a sample temperature and obtain a rotational viscosity) of 0 to 01 to 100 Pa · s. The second benzene of the present invention. The compound was subjected to a rotational viscosity obtained by an E-type adhesive 322229 28 201113245 degree at 5 〇t (using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) to measure a sample of about 1.2 ml at a sample temperature of 50 ° C. 01至80Pa. s, more preferably 0. 01. The value of the value of the rotational viscosity is preferably 80 Pa. s or less, more preferably 70 Pa. s or less, more preferably 60 Pa · s or less, preferably 0.01 to 80 Pa. s, more preferably 0.11.至更优选为为0. 1至2Pa。 s, preferably 0. 1 to 2Pa. s. The method of adjustment is as described above, for example, to 70 Pa · s. Preferably, benzaldehyde and/or benzaldehyde is selected, and benzaldehyde is more preferably selected as the aromatic aldehyde compound in the present invention, relative to the molar number of furfural in the present invention.至1.1至1. The first embodiment of the present invention is more preferably adjusted to 0. 1 to 1. 0 or other, as is well known in the art, for example, a distribution of the number of repeating units represented by the general formula (1) as described above or a repeating unit represented by the general formula (2) The distribution of the number is narrowed in the direction of the narrowing; or the phenolic compound of the present invention is adjusted so that all the aldehydes are added in an amount of from 0.01 to 0.4 mol per gram of the phenol in the present invention. The number average molecular weight of the second phenolic compound of the present invention obtained by the E-type viscosity meter at 50 ° C can be carried out in the following manner as in the case of the first phenolic compound of the present invention: The number of moles of the aromatic aldehyde compound in the present invention is adjusted with respect to the molar number of furfural in the present invention; or the like, as is well known in the art, for example, to enable The distribution or general formula of the number of repeating units represented by the general formula (1) (2) adjusting the direction in which the distribution of the number of repeating units is narrowed; or adjusting according to the method of adding 29 322229 201113245 to the wire of the present invention to make the whole material class Q Q1u.4 Moh Adjusting the average molecular weight of the benzene-aged compound of the present invention. Due to the second benzoin compound of the present invention, the rotational viscosity obtained by the E-type viscometer in the 5th generation is in the range of 〇〇1 to ι〇〇ρ& In the range, when the liquid state is exhibited at 50 C (in the state where the sample temperature is not crystallized at 5 ° C), the second benzene compound of the present invention will be used. The stupid varnish resin is particularly good in the W-movement which is added to the semiconductor element, and thus can be suitably used as a sealing material or an underfill material for a semiconductor. 1st, the first and/or second benzoquinone-based compound obtained in the present invention can be directly used as a curing agent for the fluorene tree, and can be used for a binder, a coating material, a laminate material, a molding material, or the like. It is produced by reacting with epichlorohydrin (hereinafter referred to as an oxy-resin derived from the benzene compound of the present invention). Further, it is also possible to use a hardened material such as this. The epoxy resin obtained in this manner is excellent in fluidity when the material is processed on a semiconductor element, and is preferably used as a sealing material or a bottom filling material for a semiconductor element because it is excellent in heat curing. ^ The first and/or second benzophenone compound of the present invention is mixed with an epoxy resin which is derived from an epoxy resin derived from the phenol compound of the present invention. P can produce an epoxy resin composition. Further, in the epoxy resin composition, a hardening accelerator or other additives may be added to the sergeant. The epoxy eucalyptus composition obtained in this manner is suitable for the flow of the material on the semiconductor element 322229 30 201113245, and it is suitable for the characteristics of the sealing material for the semiconductor element after the heat curing. Use as an Ah i silk filling material. As the oxime and/or ro added to the present invention, the oxygen resin is preferably a stupid-oxygen resin derived from the present invention as the ring outside the aforementioned ring derived from the soil compound of the present invention. Oxygen trees are ancient and ancient, I

Epoxy resin: 曱: phenolic dibisphenol A epoxy resin, bisphenol F f oxy resin, stupid varnish type % Oxygen erythraea, trisphenol decane type epoxy 1 glyceryl screaming type Epoxy tree month, end 匕廿: conjugated epoxy resin, etc., w^ fine (four) county purpose, shrinking water == oxygen resin, functional epoxy resin, etc. Epoxy resin. There is no problem with these epoxy resins when used. The preferred epoxy resin other than the above epoxy resin and the ancient product 4 sister ° make the clothing rolling rouge composition low viscosity == look, can be exemplified: in 25t under the liquid state of the double A clothing, 曰 925C A double F-type epoxy resin in a liquid state. An epoxy resin composition containing an epoxy resin derived from the phenpanic compound of the present invention and an epoxy resin (except for the first and/or second benzoin compounds of the present invention) The viscosity is low, and it is preferable from the viewpoint that the viscosity of the epoxy resin composition is also low. The epoxy resin composition may be exemplified by a benzene-setting varnish resin, a viscous varnish resin, a benzene resin, a biphenyl-based resin, a naphthoquinone varnish resin, and a cashew nut ( Cashew) secret varnish resin, propyl benzoquinone varnish resin' and more preferably benzene (tetra) acid varnish resin, phenolic varnish resin, benzene aryl resin, biphenyl aryl resin, propyl 322229 31 201113245 =_clear, fat, and better boring _ varnish • a base resin, phenylene aralkyl paper 5 phenol aralkyl a lacquer resin for the aforementioned hardening accelerator. The first and/or the second stupid _, the combination: =: =: the second hair: _ # 卜 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Among them, from hard, 'J&quot;, imidazoles and tetracene thereof are preferably 2-ethyl-4-methylimidazole in a liquid state on both sides or in a lower state. The reverse: the second stupid compound and the gas in the gas into the __中添===言二: in the presence of the benzene: in the presence of metal cerium oxide, in the 5Q to 15 generation, preferably in the main A method in which the range of C is carried out for about 1 to 1 hour. This = relative to the secret equivalent of the secret varnish resin, the amount of epichlorohydrin is from 2 to 15 moles, preferably from 2 to 10 moles. Further, the amount of the metal hydroxide to be used is 〇·8 to I 2 times the molar amount, preferably 0.9 to LU rpm, relative to the benzene varnish resin base equivalent: In the post-treatment, after the reaction is completed, the excess alcohol is distilled off, and the residue is dissolved in an organic ridge agent such as methyl isobutyl ketone, filtered and washed with water to remove inorganic salts, followed by distillation. In addition to the organic solvent, the desired epoxy resin can be obtained. The fat can be obtained by mixing the oxy-resin derived from the phenol-based compound of the present invention with a general secret varnish resin in this manner to obtain an epoxy resin and a product. Further, an epoxy resin derived from the benzene=compound of the present invention obtained by reacting the above-obtained ninth and/or 32 322229 201113245 and 2 benzene compounds of the present invention with a surface alcohol can also be used. Inventive No. I or second benzene test system. Compounds are mixed to obtain an epoxy resin composition. In the epoxy resin composition, 'can be added as needed> machine filler = mold release agent, colorant, coupling agent, flame retardant, and the like. When it is used for the purpose of +conductor sealing, it is preferably a f-machine filling material from the viewpoint of improving thermal conductivity. Examples of such an inorganic filler include non-defective dioxotomy, crystalline dioxotomy, oxidized melody, (four), carbonic acid A, talc, mica, barium sulfate, etc. Oxide dioxide, twinning, etc. Further, the ratio of the additives may be the same as that in the epoxy resin composition for semiconductor sealing. The two-body sealing material includes a sealing material i that seals the gap between the semiconductor and the circuit board and the periphery of the semiconductor element, and seals the gap between the member and the circuit board. The latter is generally referred to as the underfill material. In the present invention, the filling material 'and the sealing material' may be in the form of a solid such as a liquid, a paste (_), or a tablet. The epoxy resin composition can be obtained by, for example, curing the epoxy resin composition, for example, in (10) to (10). Further, a method of semi-conducting a semiconductor resin composition (4) semiconductor is used to obtain a method for hardening a gap between the semiconductor and the circuit substrate by the epoxy resin assembly. Or a method of causing the epoxy resin composition to flow into the gap between the semiconductor and the circuit substrate and the semi-conducting = 322229 33 201113245 and curing the epoxy resin composition. In the present invention, the sealing of the semiconductor element means 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 a gap included in the semiconductor element and the circuit substrate. And a step of injecting a sealing material around the semiconductor and a step of hardening the sealing material. [Examples] Hereinafter, the examples and comparative examples will be described to more specifically illustrate the inner valley of the present invention. However, the invention is not limited by the examples. Also, "parts" in this document means the meaning of parts by weight. [Example 1] In a glass four-necked flask equipped with a thermometer, a feed/distillation port, a cooler, and a stirrer, 670 parts (5.0 mol) of o-allylphenol and 30. 5 parts of 25 25 moles, and 4 parts of a 25% aqueous sodium hydroxide solution added as an alkaline catalyst was added dropwise, and the reaction was carried out at 11 Torr for 18 hours, and then cooled to 30 ° C. 0份下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下下The reaction was carried out for 4 hours, and 500 parts of pure water of 90 C or more was charged and washed with water, and then heated to 165 ° C and dehydrated to remove unreacted components by a reduced pressure treatment. The obtained liquid benzene was varnish resin at 5 (The rotational viscosity at TC was 3.2 Pa·s. [Example 2] O-allylphenol was placed in a four-necked flask equipped with a thermometer, a feed/distillation port, a cooler, and a stirrer. 670 parts (5.0 mo 34 322229 201113245 ears), willow Ik 3 0. 5 parts (〇. 2 5 moles), and added 40 parts of 25% sodium hydroxide solution added as an inert catalyst, at ii (Tc The reaction was carried out for 18 hours. After that, it was cooled to 30 ° C. Neutralization was carried out using a 25% aqueous solution of hydrochloric acid, and the addition force σ 42% - 17.1 parts (0.25 mol), as an acidic catalyst. Oxalic acid 6. γ parts, and the reaction was carried out at 110 ° C for 10 hours, and 9 Torr was added. (: 5 parts of the above pure water was washed with water, and then heated to 165. (: and dehydration, by decompression treatment to remove unreacted components. The obtained liquid phenol novolak resin has a rotational viscosity of 4. OPa.s. [Example 3] 5份(0. 25摩尔) Adding allylic phenol 670 parts (5.0 moles), 42% furfural water 17.9 parts (0. 25 moles) into the glass inlet four-necked flask of the inlet / outlet, the cooler and the mixer. 5份(0. 25摩尔) After the reaction was carried out for 8 hours, the reaction was carried out at a temperature of 3 ° C. After the reaction was carried out for 8 hours. 60 parts of a 25% sodium hydroxide aqueous solution as an alkaline catalyst, and reacted at 11 〇 °c! 8 hours ' neutralized with 25% hydrochloric acid aqueous solution, and put 9 (500 parts of pure water of TC or more, And the viscous viscosity at 50 ° C is 4. 3Pa . s. The viscous viscosity at 50 ° C is 4. 3Pa . s. [Examples 4 to 7] Except for those shown in Tables 1 and 2, the same procedure as in Example 1 was carried out. [Example 8] A thermometer, feed/distillation was provided. Port, cooler and mixer 35 322229 201113245 glass four-necked flask, placed 670 parts of o-allylphenol (5. 〇mol), lysaldehyde 18.3 parts (0·15 mol), and drops 134 parts of a 25% hydrochloric acid aqueous solution added as an acidic catalyst was added, and the reaction was carried out at 110 ° C for 30 hours, and then cooled to 30 ° C. Then, 25 parts of furfural water (25 ml) was added thereto. The reaction was carried out at 100 ° C for 24 hours. In the reaction product, 12% (0. 018 moles) of unreacted salicylaldehyde residue was found. Into the reaction product, 500 parts of pure water of 90 ° C or higher was placed, and the mouth was washed with water. Then, the temperature was raised to 165 ° C and dehydrated, and the unreacted component was removed by a reduced pressure treatment. 5Pa · s. The resulting viscous viscous resin is 0. 5Pa · s. [Example 9] In a glass four-necked flask equipped with a thermometer, a feed/distillation port, a cooler, and a damper, o-allyl phenol 629. 8 parts (4 7 mol), benzoquinone was added. The acid was 38.5 parts (0.36 parts) and was added dropwise to a solution of 28.5% of a 50% aqueous sodium hydroxide solution as an inert catalyst, and after 18 hours of anti-deer under 1351, it was cooled to 30 °C. Neutralization was carried out using a 25% aqueous hydrochloric acid solution, and 8 6 parts of formaldehyde water (8.62 parts) was added as 25% of an acidic catalyst: 1.0 part of an acid aqueous solution and reacted at 1 ° C for 1 hour. The product was neutralized with a 25% aqueous solution of sodium hydroxide, and 5 parts of pure water of 90 ° C or higher was added and washed with water. Then, the temperature was raised to 165 ° C and dehydrated, and the unreacted component was removed by a reduced pressure house. The kinetic viscosity of the obtained liquid phenol novolak resin was 1. 〇3 Pa · s. [Examples 10 to 13] Except for those shown in Table 3, the rest were carried out in the same manner as in Example 9 322229 36 201113245. ' [Comparative Example 1] Adding o-allyl (4) parts to a glass four-necked flask equipped with a thermometer, a feed/heel exit, a cooler, and a stirrer (5 〇 Mo ^ W Π.9 Rail 25 material), material catalyst: 6.7 parts, reacted under air for 5 hours, put 500 parts of pure water above the sputum, and washed with water, then warmed to the boot and dehydrated at the decompression point (4) to remove unreacted age. Turn (10) facial varnish; the rotational viscosity of the fat at 50 C is i. ipa · s. 'Comparative Example 2>> Except as shown in Table 4, it was carried out. The remainder was synthesized in the same manner as in Example 1 according to the example of the prior art document 2, in which a polyalkenyl compound (paraben (hydroxyallylphenyl) decane type phenolic acid varnish resin) was synthesized. <Synthesis of phenol (hydroxyphenyl) decane type phenol novolak resin> 400 parts of phenol was placed in a four-necked glass flask equipped with a thermometer, a feed/spray outlet, a cooler, and a transfer machine (4) · 26 moles · Liu / 47. 2 parts (0.38 moles), and 1 part of p-toluenesulfonic acid, reacted under a nitrogen gas stream at 130 ° C 'cooled to 95 Ϊ. After neutralization in a 25% sodium hydroxide solution, the mixture was poured into 4 parts of pure water at 90 ° C or higher, and washed with water and water. Then, the internal temperature was raised to 150 ° C, and the unreacted component was removed by steaming-steaming. The obtained resin was a solid, and the melt viscosity at 150 ° C was 〇 9 Pa · s. 322229 37 201113245 [Comparative Example 3] <Synthesis of styrene-based styrene resin of benzoate-based styrene resin> In ', with / with a degree of rinsing, feed / hall exit, cooler and In a glass four-necked flask of a stirrer, the ginseng ((tetra)phenyl) which was produced in the above-mentioned manner was placed in a (10) part of a styrofoam resin and 250 parts of 2-propanol, and after the sandalization was evenly distributed, Into the sodium hydroxide 40. 7 parts (1.02 mol), and then continue (four) 1 hour. After adding 796 parts of propyl propyl fluoride (1_02 mol) dropwise for 1 minute, the reaction was carried out for 5 hours under the step to complete the dilute propyl mystery. After the 2-propanol was removed, 5 parts of the pure water above the cockroach was poured, and the salt produced in the field was washed with water. The temperature was raised to 19 °c, dehydrated, and the bench was mixed for 6 hours to implement Claisen rearrangement. The obtained resin was semi-solid, and it was 5 〇 (5 (: the rotational viscosity was 170 Pa · s or more. [Comparative Example 4 ] The glass was provided with a thermometer, a feed/distillation port, a cooler, and a stirrer. In the flask, 629. 8 parts (4 7 moles), 51.4 parts of phenylfurfural (〇·49 moles) were placed, and a 25% aqueous sodium hydroxide solution added as an alkaline catalyst was added dropwise. 77·6 parts, at 135. (: After performing the reaction for 18 hours, 'cooling to 30 ° C', neutralization was carried out using a 25% aqueous hydrochloric acid solution, and 5 parts of pure water at 90 ° C or higher was added and washed with water. The temperature is raised to 165 C and dehydrated. The unreacted component is removed by a reduced pressure. The obtained liquid benzene is expected to have a varnish resin at 5 Å. (The rotational viscosity is 12.6 Pa · s. The phenol obtained in the present invention. The analysis method of the compound and the hardener is as follows: 38 322229 201113245, (1) The point obtained by the e-type viscometer at 5 (TC) The E-type viscometer is a TVH type manufactured by Toki Sangyo Co., Ltd. .. put the sample into the cup attached to the E-type viscometer, and put: 匕 cup to the cup 5 c Set in the strange temperature tank and liquid feeding device (F25-MP made by Jiaxin Company). · Use the E-type viscometer to start the measurement of the rotational viscosity of the above sample, and when the indication value of the suspected turning viscosity is stable The value of the rotational viscosity. In the table, 'this value is listed in the item of "E-type viscosity". (2) 〇H equivalent (summary) Use ethane to make acetonitrile, and use excess B chlorine to decompose with water. And use the test to perform the titration method) • Accurately weigh the sample lg, and add the i, 4_ dipole ship to dissolve it. ^ After the '^' solution, add 1.5 m / liter of B Helium/anhydrous sulphate> sulphate lOinl and cooled to q°c. • Add pyridine 2mi and react in a water bath of 6〇±rc for 1 hour. Cool down after reaction and add 25ml of pure water. After thoroughly mixing, it is used to decompose acetonitrile. • Add 25 ml of acetone and phenolphthalein. Use 1 mol/L of potassium hydroxide solution and titrate until the sample solution is reddish purple. If there is no sample, perform the measurement at the same time as above. Calculated by the following formula 0H equivalent is obtained. 0H equivalent [g/eq.] = (l〇〇〇xW)/(fx(BA)) 322229 39 201113245 Here, W, f, B, and A are each as follows. Sample weight [g] f : 1 mol / liter of potassium hydroxide aqueous solution factor = 1. 002

B: the amount of 1 mol/liter potassium hydroxide aqueous solution consumed in the blank measurement [ml JA: the amount of 1 mol/liter potassium hydroxide aqueous solution consumed in the measurement of the sample [ml] (3) water absorption rate Determination • In the mold, harden it at 15 (TC for 5 hours at 18 〇. (: Let it harden for 8 hours to form the sample. Size; (Φ50 ± 1) χ (3 ± 0 · 2) (diameter X thickness; with) • Wipe the surface of the sample cleanly and measure the weight of the sample. Place the sample in a 100 ml sample vial and add 8 μl of pure water. At 95 ° C In the hot air circulation drier, let it absorb water for 24 hours. Then 'k dry and take out, soak it in the low temperature strange temperature water tank for 25X:. • After cooling, wipe off the moisture attached to the surface and measure the weight. Calculate according to the following formula to determine the water absorption rate (water absQrpti〇n). Water absorption rate [%K(BA)/A)xl〇〇A. Weight before water absorption [g] B: Weight after water absorption [g] (4) The measurement of the glass transition temperature (Tg) was carried out by hardening the mold at 15 ° C for 5 hours, and the sample of the &lt;, tM, time was cut into the following dimensions to prepare a sample. 40 201113245 Dimensions: (50 soil 1) x (40 ± 1) x (l 〇〇 ± l) (longitudinal X lateral X height; mm) • Measuring device, set the sample to TMA_60 (Shimadzu (Shimadzu)) • Measured in a N2 (nitrogen) environment. • Temperature rise rate; measured at a rate of 3^/min to 350. (:, to find the temperature of the inflection point as the glass transition temperature (Tg) (5) Determination of gelation time (gei time). Put the epoxy resin composition described in Tables 5 to 8 into a test tube, and / / / in a 150 C oil bath (01i bath), press 1 The epoxy resin composition was stirred at intervals of one second using a glass rod. The time during which the resistance of the agitation was increased was measured as the gelation time. (6) Mechanical properties of the cured product (elasticity, displacement, strength (stress) measurement • The sample was subjected to 丨5〇 in a mold. (: The sample was allowed to harden for 5 hours and hardened at 180 ° C for 8 hours, and cut into the following dimensions to prepare a sample. Size: (75 ± l) x(6±l)x(4±l) (longitudinal X transverse x thickness; 匪) 'There is an automatic green machine (aut〇graph) (Model: AG-5000D Shimadzu) Head speed: 2. Omm/min, distance between 2 o'clock: 〇Computed with a compression bending test (c〇mpressi〇n bending test). (7) Determination of the number average molecular weight Under the conditions described, gel permeation chromatography (GPC) was carried out to obtain a number average molecular weight (??). *Nongfang: Gelto Permeation Chromatograph (HLC-8020) made by Tosoh Corporation 41 322229 201113245

.column; connected in series with TSKgel G2000HxL 4, G3000HxL and G4000HxL each; • lysate; tetrahydrofuran • solution flow; 1. 〇ml/min • column temperature; 40° C • Detection method; visible light detector (UV (ultraviolet light)). Calibration curve; using standard polystyrene material to prepare the phenolic compound in the examples and comparative examples, and the resulting phenol The properties of the compound are shown in Tables 1 to 4. Further, in Tables 1 to 4, the n/m composition ratio indicates the number of repeating units represented by the general formula (1) / the number of repeating units represented by the general formula (2), that is, the aromatic aldehyde compound of the present invention. Molar number / Molar number of furfural in the present invention. , Table 4 . — Viscosity is solid and semi-solid' means that the viscosity cannot be determined because the phenolic compound is not dissolved in C. The epoxy resin composition was obtained by using the benzene-based compound obtained in the examples and the comparative examples as a curing agent, an oxygen resin and a curing accelerator. For the above-mentioned enamel tree, the use of Japanese epoxy resin ==! liquid:: oxygen resin, epoxy equivalent - said Ami ^. Guohuacheng (share) system 2 ships (2~ethyl-4-jiaxin heart sitting). The foregoing epoxy resin composition =:, stupid__ is:::: The epoxy resin composition is heated to 15 (TC is then mixed with 322229 42 201113245, vacuum defoamed and cast on heated To l5 (in the mold of rc, it is hardened at 15 5 for 5 hours' and hardened at 180X: for 8 hours to obtain an epoxy resin. The blending and physical properties of the obtained epoxy resin cured product 'Merge is shown in Tables 5 to 8. In Tables 5 to 8, α 1 is the line % expansion coefficient of the temperature below the glass transition temperature (Tg) and α 2 is the glass transition temperature (Tg). The linear expansion coefficient at the above. In Tables 5 to 8, the displacement is the displacement at the time of fracture of the specimen in the compression bending test, and the strength is the stress in the compression bending test. [Table 1] f~·' ~ ----_, Example 1 Example 2 Example 3 Example 4 Synthesis conditions Phenol compound (mol) o-allylphenol (5.00) o-allyl phenol (5. 00) o-allylphenol ( 5.00) o-allylphenol (5. 00) aromatic aldehyde compound (mol) salicylaldehyde (0.25) salicylaldehyde (0·25) salicylaldehyde (0.25 mg) salicylaldehyde (0.35) Mol) 42% Aldehyde water (0.25) 42% formalin (0.25) 42% formalin (0.25) 42% formalin (0.15) Alkaline catalyst type sodium hydroxide sodium oxide sodium hydroxide sodium hydroxide acid catalyst type hydrochloric acid oxalic acid Hydrochloric acid n/m composition ratio 1.0 1.0 1.0 2.33 Character E-type viscosity (Pa · s / 50 ° C) 3.2 4.0 4.3 58.1 0H equivalent (g / eq) 150 152 142 152 number average molecular weight (-) 500 514 518 549 43 322229 - Example 5 Example 6 Example; Example 7 Example 8 Synthetic conditions Phenol compound (mol) o-allyl^&quot; (5.00) o-propyl propyl benzene (4.70) o-propyl benzophenone (7.50) O-allylphenol (5. 00) Aromatic compound (mol) Salicylaldehyde (0.15) Salicylaldehyde (0·24) Salicylaldehyde (0.35) Salicylic acid (0·15) Furfural (mol) 42% Formaldehyde water (0. 35) 42% formalin (0. 25) 42% formalin (0.15) 42% formalin (0. 35) Alkaline catalyst type sodium hydroxide ^ sodium hydroxide sodium hydroxide Medium type hydrochloric acid hydrochloric acid hydrochloric acid n/m composition ratio 0.43 0.94 2. 33 0.43 trait E-type viscosity (Pa · s / 50 ° C) 0.6 3.0 20.0 0.5 0H equivalent (g / eq) 171 151 151 166 number average Amount of sheep (-) 480 507 510 479 201113245 [Table 2] [Table 3] Example 9 Example 10 Example 11 Example 12 Example 13 Synthesis conditions Phenol compound (mol) o-allylphenol (4.70) o-olefin Propylphenol (4.70) o-allylphenol (5.00) o-allyl phenol (4.50) o-allyl phenol (3.75) aromatic aldehyde compound (mol) clumaldehyde (0.33) benzofural (0.24) Benzaldehyde (0.25) benzaldehyde (0.25) benzaldehyde (0.25) formaldehyde (mol) 42% furfural water (0.12) 423⁄4 formalin (0.25) 42% furfural water (0.25) 42% formalin ( 0.25) 42% formalin _ (0.25) Alkaline catalyst type sodium hydroxide 氪 纳 氢氧化 氢氧化 氢氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氢氧化钠 氢氧化钠 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 0 0 0 0 1.0 Character E-type viscosity (Pa-s/50°C) 1.03 0.49 0.45 0.46 0.63 OH equivalent (g/eq) 183 166 168 166 168 Number average molecular weight (I) 502 489 504 503 518 44 322229 201113245 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Synthesis conditions Phenol compound (mol) o-allylphenol (5.0 00) o-allylphenol (5.00) — o-allylphenol (4. 70) aromatic aldehyde compound (mol) — salicylaldehyde (0.25) — clitofuraldehyde (0.36) methyl (mol) 42% furfural water (0.25) – A type of alkaline catalyst - sodium hydroxide - sodium oxyacid catalyst type oxalic acid - - n / m composition ratio - — — trait E-type viscosity (Pa · s / 50 ° C) 0.1 solid semi-solid 12.6 OH Equivalent (g/eq) 142 134 160 207 Number average molecular weight (-) 465 602 608 512 [Table 5] Example 1 Example 2 Example 3 Example 4 Preparation of epoxy resin (parts) 100 100 100 100 Benzene age system Compound (part) 80.7 81.7 76.3 81.7 Hardening accelerator (parts) 0.25 0.25 0.25 0.25 Physical gelation time (min/150 °C) 10 10 9 9 Water absorption (%) 1.5 1.5 1.7 1.4 Tg(°C) 92 92 91 104 ai (ppm) 81 77 86 81 a 2 (ppm) 192 192 191 191 Elasticity (MPa) 3057 3095 2816 2946 Displacement (mm) 9 7 10 10 Strength (MPa) 117 112 112 118 45 322229 201113245 [Table 6] Example 5 Example 6 Example 7 Example 8 Preparation of epoxy resin (parts) 100 100 100 100 Phenolic compound (part) 91.9 81. 2 81.8 89.3 Hardening accelerator (parts) 0.25 0.25 0.25 0.50 Physical gelation time (min/150 °C) 14 10 13 12 Water absorption (%) 1.6 1.5 1.4 1.8 Tg (°C) 78 92 98 72 ai (ppm) 84 80 81 67 a 2 (ppm) 202 191 193 219 Elasticity (MPa) 3085 3040 2981 3153 Displacement (leg) 5 9 9 8 Strength (MPa) 89 115 117 107 [Table 7] - Example 9 Example 10 Implementation Example 11 Example 12 Example 13 Preparation of epoxy resin (parts) 100 100 100 100 100 Hardener (parts) 98.4 89.2 90.1 89.2 90.1 2E4MZC%, relative to epoxy resin 0.50 0. 50 0.50 0.50 0.50 Physical gelation time (min/150 ° C) 17.2 11.4 11 13 10 Water absorption (%) 1.40 1.56 1.47 1.49 1.45 Tg (°C) 102 93 96 96 93 ai (ppm) 71 71 76 75 75 a 2 (ppm) 220 187 211 205 214 Elasticity (MPa) 2742 2879 2687 2797 2682 Displacement (mm) 1.7 8.1 8.1 7.9 7.9 Strength (MPa) 28 104 103 108 106 46 322229 201113245 [Table 8] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Preparation ring Oxygen resin (parts) 100 100 100 100 Hardener (parts) 76.3 72.0 89.3 111.3 2Ε4ΜΖ (%, relative to epoxy tree ) 0.25 0.25 0.50 0. 50 Physical gelation time (min/150°C) 13 — 12 7. 1 Water absorption (%) 1.6 1.5 1.8 1.36 Tg(°C) 67 127 72 104 a:i(ppm) 83 78 67 78 o: 2 (ppm) 185 184 219 229 Elasticity (MPa) 2770 2620 3153 3173 Displacement (mm) 8 12 8 2.3 Strength (MPa) 95 120 107 44 From the results of the above examples, it is known in the examples Each of the epoxy resin compositions produced is a sealing material or an underfill material used as a semiconductor element. [Simple description of the diagram] Benefits [Main component symbol description] None 47 322229

Claims (1)

201113245 VII. Patent application scope: 1. A phenol-based compound obtained by reacting a phenol represented by the general formula (6), an aromatic aldehyde compound represented by the general formula (7), with formaldehyde, and the phenol, The aromatic aldehyde compound and/or the phenol compound obtained by polycondensing the formaldehyde, the reaction is carried out by any one of the following methods: using the phenol, the aromatic acid compound, and the citric acid a method of preparing a phenol-based compound by reacting the phenol with the aromatic aldehyde compound, and then reacting the phenol with the formaldehyde to obtain the phenol-based compound; or a method in which a reaction product obtained by reacting an aromatic aldehyde compound and a reaction product obtained by reacting the phenol with the furfural are reacted to obtain the aforementioned benzene-based compound, and, in the foregoing reaction, 0倍摩尔, and the above-mentioned aromatic aldehyde compound is 0. 1 to 4. 0 times the molar, and Such that the benzene compound trypan 5〇 ° C at a rotational viscosity of the resulting square is an E-type viscometer. 〇1 to be adjusted by way of l〇〇pa.s (wherein, f represents an integer of 0 to 3, R7 represents a hydrogen atom, a linear or branched alkyl group which may have 4S 322229 201113245, a carbon number of 1 to 4 of the substituent, an allyl group which may have a substituent Either if r is 2 or more, each R7 can be • the same or different, CHO (wherein b and c represent an integer of 〇 to 3, and R8 may be the same or different, and represent a hydrogen atom, a linear or branched alkyl group having a carbon number of 4 to 4 which may have a substituent, may have a substituent Any one of allyl groups, if b is 2 or more, each R8 may be the same or different). 2. The phenolic compound according to claim 1, wherein the reaction is carried out by reacting the phenol with the aromatic aldehyde compound and then reacting with the formaldehyde to obtain the phenol compound. When the method is carried out, the benzene age is reacted with the aromatic compound in the presence of an inert catalyst, and then reacted with the furfural in the presence of an acid catalyst. 3. The phenolic compound according to the invention of claim 2, wherein the phenol is o-allylphenol. 4. The phenolic compound according to any one of the preceding claims, wherein the aromatic compound is a phenolic compound or a phenolic compound. a repeating unit represented by the general formula (1) and a repeating unit represented by the following general formula (2) as a main constituent unit of a phenol compound, 322229 49 201113245 The phenolic compound has a number average molecular weight of 400 to 600, and the benzene 01至lOOPa · s The rotational viscosity of the compound obtained by the E-type viscometer at 0 0 ° C is 0. 01 to lOOPa · s (Formula, a, b, and c each independently represent an integer of 0 to 3, a ruler and R2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and may have Any one of the allyl groups of the substituent, if a or b is 2 or more, each R and each r2 may be the same or different) (Formula d' represents an integer of 〇 to 3, and R3 represents any of a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and a dilute propyl group which may have a substituent. If d is 2 or more, each r3 may be the same or different). 6. A benzene-aged compound according to claim 5, in the pot, in the general formulae (1) and (2), and/or R3 is an allyl group. ',, 7 · If you apply for supplement _ Item 5 or the sixth rhyme benzene (IV) compound, where 'the general formula (1) represents the repeating unit, is the following general formula (4) 322229 50 201113245 or / and the following formula ( 5) Representation of the repeating unit: (wherein, a represents an integer of 0 to 3, and R&gt; represents a hydrogen atom, a linear or branched alkyl group which may have a substituent of 5 to 1 or 4, and an allyyl group which may have a substituent If a is 2 or more, each Ri may be the same or different), (wherein 'a represents an integer of 0 to 3, and R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and any of fluorenyl groups which may have a substituent" When a is 2 or more, each r1 may be the same or different. 8. A method for producing a phenol-based compound, wherein the phenol-based compound is obtained by reacting phenol represented by the general formula (6-1) and an aromatic aldehyde compound represented by the general formula (7-1) with formaldehyde. The phenol, the aromatic aldehyde compound, and/or the acetal are polycondensed, and the phenol compound is produced by reacting the phenol with the aromatic aldehyde compound in the presence of a basic catalyst 322229 51 201113245, and then 0倍摩尔,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, And adjusting the viscosity of the above-mentioned aldehyde-based compound to be 由. 01 to l〇〇pa. S by the E-type viscosity meter at 5 ° C. (6-1) (wherein, f-Ι represents an integer of 0 to 3, and R7-1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, may have a substituent Any one of the allyl groups, if f - 丨 is 2 or more, each R7 〗 may be the same or different), CHO 卜, (7~" (wherein b_l, c-1 represents 〇 to 3) The integers, which may be the same or different, represent a hydrogen atom, a straight or branched filament having a carbon number of 4, which may have a substituent, and an allyl group which may have a substituent such as b] is 2 In the above case, each R8·1 may be the same or different. The epoxy resin is obtained by reacting the benzene (tetra) compound described in the scope of claims 1-4 to 312229 to obtain 322229 52 201113245 r • 10. An epoxy resin composition containing the phenolic compound and epoxy resin according to any one of claims 1 to 7. - 11. An epoxy resin a composition comprising a phenol resin (except for the phenolic compound) and an epoxy resin according to claim 9 of the patent application. a cured product obtained by hardening an epoxy resin composition as described in claim 10 or 11. 13. A sealing material for a semiconductor component, which is claimed in claim 10 or An epoxy resin composition according to item 11. 14. An underfill material for a semiconductor device, which is obtained from the epoxy resin composition according to claim 10 or 11. A semiconductor device which is sealed using the sealing material described in claim 13 or the underfill material described in claim 14. 53 322229 201113245 IV. Designated representative figure: No picture in this case (1) The representative representative of the case is: (). (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case does not represent the chemical formula 322229