TWI415911B - Biphenylene cross-linked phenol novolac resin and the use thereof - Google Patents

Abstract

Biphenylene-bridged phenol novolak resins represented by the general formula (2), which consist of products of reaction of a biphenyl compound represented by the general formula (1) with a phenol mixture containing at least one dihydric phenol: (1) (wherein X is alkoxy having 1 to 4 carbon atoms or halogeno) (2) (wherein R<SUP>1</SUP>, R<SUP>2</SUP> and R<SUP>3</SUP> are each independently substituted or unsubstituted, linear or branched alkyl having 1 to 10 carbon atoms or substituted or unsubstituted aryl, with the proviso that R<SUP>1</SUP>'s, R<SUP>2</SUP>'s, and R<SUP>3</SUP>'s may be each the same or different from each other; p1 and p3 are each an integer of 1 to 4; p2 is an integer of 1 to 3; n is an integer of 0 to 15; m1, m2 and m3 are each an integer of 1 or 2 and m2's may be the same or different from each other, with the proviso that a case wherein all of m1, m2 and m3 are 1 and a case wherein all of m1, m2 and m3 are 2 are excepted).

Description

Stretched phenyl crosslinked novolac resin and its use

The present invention relates to a stretched phenyl crosslinked novolak resin obtained by reacting a bis(alkoxymethyl)biphenyl or bis(halogenated methyl)biphenyl with a phenolic mixture containing at least one dihydric phenol component. The novolac resin of the present invention can be used as a epoxidizing varnish resin or a raw material of an isocyanated urethane resin, a triazine resin or a polyester resin, in addition to being used as a curing agent for an epoxy resin.

In the past, a novolac resin obtained by reacting bis(alkoxymethyl)biphenyl or bis(halogenated methyl)biphenyl with a phenol revealed various uses of a bis(methoxymethyl)biphenyl compound. A biphenyl-crosslinked novolac resin having a structure or a mixture of the above (Patent Document 1).

When the above-mentioned extended phenyl crosslinked novolac resin is used as a curing agent for an epoxy resin, hardening with superior low water absorption (low hygroscopicity), flame retardancy, mechanical properties, adhesive properties, and the like can be obtained. Things.

However, the extended phenyl crosslinked novolak resin of the prior art has a problem that the curing speed is slow as compared with the novolak resin. If the hardening speed is slow, the hardening time becomes long, and when used for each purpose, it has an adverse effect on productivity or production cost. Therefore, it has been desired to develop a stretched phenyl crosslinked novolac resin which satisfies low water absorption (low hygroscopicity), flame retardancy, and high heat resistance, and has a high curing rate.

[Patent Document 1] Japanese Patent Publication No. 08-143648

The object of the present invention is to provide a curing rate of epoxy resin which has low water absorption (low hygroscopicity), heat resistance, flame retardancy, mechanical properties, and adhesive properties and is superior to the prior art extended phenyl crosslinked novolak resin. Fast bisphenyl crosslinked novolac resin.

In order to achieve the above object, the present inventors have found that a bisphenylene crosslinked novolac resin containing at least one dihydric phenol component in a phenol is effective as a result of intensive studies, and thus the present invention has been completed.

In other words, the present invention relates to a biphenyl represented by the following formula (2) which is obtained by reacting a biphenyl compound represented by the formula (1) with a phenol mixture containing at least one dihydric phenol component. Crosslinked novolac resin.

In the formula, X represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom,

Wherein R ¹ , R ² and R ³ may each be the same or different, and the plural R ¹ , R ² and R ³ may be the same or different, and represent a substituted or unsubstituted straight chain of 1 to 10 carbon atoms or a branched alkyl group, a substituted or unsubstituted aryl group, p1 and p3 represent an integer of 0 to 4, p2 represents an integer of 0 to 3, n represents an integer of 0 to 15, and m1, m2 and m3 each represent 1 or 2 The integer, the plural m2 may be the same or different, except that m1, m2, m3 are all 1 or all 2 except.

The extended phenyl crosslinked novolak resin obtained by the method of the invention has low water absorption (low hygroscopicity), heat resistance, flame retardancy, mechanical properties, adhesive properties, and the curing speed of the epoxy resin is higher than that of the prior art. Stretched biphenyl crosslinked novolac resin is fast and can improve productivity.

The use of the resin is exemplified as an epoxy resin curing agent or a reaction with epichlorohydrin, and is used as an epoxy resin. Further, it may be used as a flame retardant because it contains a crosslinked biphenyl crosslinking group.

Hereinafter, the present invention will be described in detail.

The phenol used in the present invention is a compound having one hydroxyl group on the benzene ring. Examples of the phenols include substituted or unsubstituted phenols, naphthols, and biphenols. In the formula (2), the substituent represented by R ¹ , R ² and R ³ may, for example, be a linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group or the like. The substituents R ¹ and R ³ may be from 1 to 4, and R ² may be from 1 to 3. Preferred alkyl groups include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and octyl groups. Specific examples are phenol; phenol, ethyl phenol, n-propyl phenol, octyl phenol, nonyl phenol, phenylphenol and other monosubstituted phenols; xylenol, methyl propyl phenol, dipropyl phenol, Disubstituted phenols such as dibutyl phenol, guaiacol, catechol ether; trisubstituted phenols represented by trimethyl phenol; naphthols such as naphthol and methyl naphthol; bisphenol, bisphenol A, bisphenol F and other bisphenols. These phenols are used singly or in combination of two or more kinds without any problem. The preferred phenols are unsubstituted phenols and meta-substituted linear or branched alkylphenols having 1 to 4 carbon atoms, more preferably phenol and m-cresol.

The dihydric phenol used in the present invention is a compound having two hydroxyl groups on the benzene ring. Specific examples are resorcinol, hydroquinone, and catechol. These dihydric phenols are used singly or in combination of two or more kinds without any problem. Resorcinol is preferred.

Further, resorcin, hydroquinone, and catechol have at least one linear or branched alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group. It is an unsubstituted compound.

Further, the dihydric phenol compound of the present invention is a group of compounds each having one hydroxyl group in the molecule, or a total of two hydroxyl groups in the benzene ring, for example, a bisphenol compound group. Specific examples of the bisphenol compound group include bisphenol, bisphenol A, bisphenol F, and the like.

These dihydric phenols are used singly or in combination of two or more kinds without any problem. Preferably, it is an unsubstituted resorcinol, hydroquinone or catechol, more preferably an unsubstituted resorcinol.

In the present invention, it is necessary to use a phenolic mixture containing at least one component of a dihydric phenol. These are considered as phenolic mixtures. The ratio of the ratio of the phenol to the dihydric phenol is not particularly limited. However, for a phenol mixture (molar number of phenols and dihydric phenols) of 100 moles, the content of the dihydric phenol is preferably from 5 to 80 moles. More preferably from 7 to 70 moles, preferably from 10 to 50 moles.

Although the diphenyl phenol crosslinked novolac resin can be obtained by using the dihydric phenol alone, it is difficult to remove the impurities in the resin production step, which is undesirable. Moreover, there is still a drawback that the water absorption rate cannot be solved.

When the diphenol-free system is completely absent, the effect of hardening speed cannot be improved.

The mixing method of the phenols and the dihydric phenol is not particularly limited, and it is preferred to mix them when the reaction is placed.

The biphenyl compound represented by the following formula (1) of the present invention may, for example, be bis(alkoxymethyl)biphenyl or bis(halogenatedmethyl)biphenyl. The compounds may, for example, be 4,4'-form, 2,2'-form or 2,4'-form isomers, preferably 4,4'-form. There is no problem in mixing two or more of these isomers.

Here, the alkoxy group is preferably an alkoxy group of an aliphatic straight-chain hydrocarbon group having 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. In terms of easiness, methoxy groups are mainly used.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferably used.

The mixture of the isomers of the bis(alkoxymethyl)biphenyl or bis(halogenated methyl)biphenyl represented by the above formula (1) of the present invention is not particularly limited in its combination and use amount, and is 4, 4 It is preferred that the body is contained as a main component.

The crosslinking agent may be reacted by whole addition, or may be synthesized by batch addition. It is added as a whole when it is better placed.

The synthetic catalyst of the present invention can be subjected to a polycondensation reaction in the presence of a Friedel-Crafts type catalyst such as an organic acid of oxalic acid, formic acid, acetic acid, and sulfuric acid, p-toluenesulfonic acid or diethyl sulfate. And synthesis.

The specific production conditions of the novolak resin represented by the general formula (2) of the present invention are as follows.

Regarding the respective isomers of the above dihydric phenol or the total amount of the mixture and the phenols, the difference of bis(alkoxymethyl)biphenyl or bis(halogenated methyl)biphenyl as a crosslinking agent The mixture ratio of the mixture or the mixture, generally, the isomer of the dihydric phenol or the mixture of the phenols is usually bis(alkoxymethyl)biphenyl or bis(halogenated methyl) The total amount of the isomer mixture of biphenyl may be 1.2 times or more, preferably 1.3 to 5.5 moles, more preferably 1.4 to 4.5 moles. When the amount is less than 1.2 times, crosslinking can be carried out, but the novolak resin which satisfies the object of the present invention cannot be stably obtained, which is not preferable. Moreover, if it is too much, the unreacted raw material will become many, and it is uneconomical.

The amount of the synthetic catalyst used in the present invention is 0.001 to 0.5 part by weight, preferably 0.001 to 0.2 part by weight, based on the total amount of the isomer of the dihydric phenol or the mixture of the phenol and the phenol. More preferably, it is suitably used in the range of 0.001 to 0.1 part by weight. When the amount used is too small, the reaction rate becomes slow, and if the amount of use is too large, the reaction proceeds fiercely, and problems such as uncontrollable reaction may occur.

Further, in the case of using bis(halogenated methyl)biphenyl, since the hydrogen halide generated has a catalytic effect, the synthetic catalyst may or may not be added.

The reaction temperature of the present invention is based on the isomer of the dihydric phenol used or a mixture of the same with a phenol and a bis(alkoxymethyl)biphenyl or bis(halogenated methyl)biphenyl as a crosslinking agent. The compounding ratio of each isomer mixture is determined, and it is usually 50 ° C to 200 ° C, preferably 70 to 180 ° C, more preferably 80 to 180 ° C. If the temperature is too low, the polycondensation reaction cannot be carried out. If the temperature is too high, the control of the reaction becomes difficult, and it is difficult to obtain the patented novolak resin.

The reaction time of the present invention depends on the reaction temperature, and usually, a condensation reaction, a methanol removal reaction or a dehalogenation reaction is carried out within 10 hours.

The reaction pressure of the present invention is usually carried out under normal pressure, and may be carried out under a slight pressure or reduced pressure.

When the polystyrene-equivalent number average molecular weight (Mn) and the weight average molecular weight (Mw) of the phenyl crosslinked novolac resin represented by the formula (2) obtained under the above reaction conditions are obtained, a broad molecular weight to a high molecular weight can be obtained. Range product. However, in view of physical properties and ease of handling, Mn is preferably from 350 to 6,800, more preferably from 500 to 3,500, most preferably from 500 to 3,000. The Mw is preferably from 350 to 20,000, more preferably from 500 to 15,000, most preferably from 500 to 13,000.

The extended phenyl crosslinked novolak resin represented by the formula (2) obtained under the above reaction conditions, wherein the number n of the crosslinked phenyl crosslinkable groups is an integer of from 0 to 15, preferably from 0 to 12. More preferably an integer from 0 to 10.

The extended phenyl crosslinked novolac resin obtained by the present invention can be directly used as a curing agent for an epoxy resin, and can also be reacted with epichlorohydrin as an epoxy resin. It can also be used as a cured product.

Further, since it contains a crosslinked biphenyl crosslinking group, it can also be used as a flame retardant.

When the extended phenyl crosslinked novolak resin of the present invention is used as a curing agent for an epoxy resin, it can be obtained by mixing the novolak resin with an epoxy resin and a hardening accelerator at a temperature ranging from 100 ° C to 250 ° C. .

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol varnish type epoxy resin, novolak type epoxy resin, trisphenol methane type epoxy resin, and biphenyl type epoxy resin. An epoxy resin having two or more epoxy groups in a molecule such as a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, or a halogenated epoxy resin. These epoxy resins are used singly or in combination of two or more kinds without any problem.

Preferred epoxy resins include cresol varnish type epoxy resins and biphenyl type epoxy resins.

As the hardening accelerator, a known hardening accelerator which hardens an epoxy resin with a phenol resin can be used. For example, an organic phosphine compound, a boron salt thereof, a tertiary amine, a quaternary ammonium salt, an imidazole or a tetraphenylboron salt can be mentioned. Among them, triphenylphosphine is preferred in terms of hardenability and moisture resistance. In order to make the fluidity higher, it is preferred to be a thermal latent accelerator which can exhibit activity upon heat treatment, preferably tetraphenylphosphonium. A tetraphenylphosphonium derivative such as tetraphenylborate is preferred.

The method for reacting the exfoliated phenyl crosslinked novolak resin of the present invention with epichlorohydrin to form an epoxy resin may, for example, be an excess of epichlorohydrin added to the novolac resin, or sodium hydroxide or hydroxide. The reaction is carried out in the presence of an alkali metal hydroxide such as potassium at a temperature of from 50 to 150 ° C, preferably from 60 to 120 ° C for about 1 to 10 hours. The amount of epichlorohydrin used at this time is from 2 to 15 moles, preferably from 2 to 10 moles, per mole of the hydroxyl equivalent of the novolak resin. Further, the amount of the alkali metal hydroxide to be used is 0.8 to 1.2 times the molar equivalent of the hydroxyl equivalent of the novolak resin, preferably 0.9 to 1.1 times the mole.

After the reaction, the reaction is carried out to remove excess epichlorohydrin after completion of the reaction, 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 distilled off to obtain the object. Epoxy resin.

The thus obtained epoxy resin and the extended biphenyl crosslinked novolak resin are used as a hardener to form a new epoxy resin composition.

The obtained epoxy resin composition may be added with an inorganic filler, a release agent, a colorant, a coupling agent, a flame retardant, or the like as necessary, or may be used after being reacted in advance. In particular, when used for sealing applications of semiconductors, it is necessary to add an inorganic filler. Examples of such inorganic fillers include amorphous cerium oxide, crystalline cerium oxide, aluminum oxide, calcium silicate, calcium carbonate, talc, mica, barium sulfate, etc., and amorphous cerium oxide. Crystalline cerium oxide or the like is preferred. Further, the mixing ratio of the additives may be the same as that in the known epoxy resin composition such as semiconductor sealing.

[Examples]

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

Example 1 is equipped with a thermometer and placed. A glass-made four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 169.2 parts (1.8 mol) of phenol, 22 parts of catechol (0.2 mol), and 4,4'-bismethoxy group. 112.6 parts (0.465 moles) of methylbiphenyl and 0.10 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, water was added to pure water (250 parts) at 90 ° C or higher for washing. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 65.3 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 773 and the weight average molecular weight (Mw) was 920 by gel permeation chromatography (hereinafter abbreviated as GPC).

Example 2 is equipped with a thermometer and placed. A glass four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 169.2 parts (1.8 mol) of phenol, 22 parts of resorcin (0.2 mol), and 4,4'-bismethoxy group. 112.6 parts (0.465 moles) of methylbiphenyl and 0.10 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 78.8 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 858 and the weight average molecular weight (Mw) was 1116 by GPC analysis.

Example 3 is equipped with a thermometer and placed. A glass-made four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 169.2 parts (1.8 mol) of phenol, 22 parts of hydroquinone (0.2 mol), and 4,4'-bismethoxy group. 112.6 parts (0.465 moles) of methylbiphenyl and 0.10 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 70.6 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 778 and the weight average molecular weight (Mw) was 930 by GPC analysis.

Example 4 is equipped with a thermometer and placed. A glass-made four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 169.2 parts (1.8 mol) of phenol, 11 parts of hydroquinone (0.1 mol), and 11 parts of catechol (0.1 mol). Ear), 112.6 parts of 4,4'-bismethoxymethylbiphenyl (0.465 moles) and 0.10 parts of 50% by weight sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 70.9 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 725 and the weight average molecular weight (Mw) was 858 by GPC analysis.

Example 5 is equipped with a thermometer and placed. A glass-made four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 178.6 parts (1.90 moles) of phenol, 11 parts (0.10 moles) of resorcinol, and 4,4'-bismethoxy group. 112.6 parts (0.465 moles) of methylbiphenyl and 0.10 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 74 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 811 and the weight average molecular weight (Mw) was 1005 by GPC analysis.

Example 6 is equipped with a thermometer and placed. A glass four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 94 parts of phenol (1.0 mol), resorcinol 110 parts (1.0 mol), and 4,4'-bismethoxy group. 112.6 parts (0.465 moles) of methylbiphenyl and 0.10 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 97 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 912 by GPC analysis, and the weight average molecular weight (Mw) was 1127.

Example 7 is equipped with a thermometer and placed. A glass four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 37.6 parts of phenol (0.4 moles), 176 parts of resorcin (1.6 moles), and 4,4'-bismethoxy groups. 112.6 parts (0.465 moles) of methylbiphenyl and 0.10 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 102 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 1006 by GPC analysis, and the weight average molecular weight (Mw) was 1234.

Example 8 is equipped with a thermometer and placed. A glass four-necked flask of 1000 parts by volume of a distillation outlet, a cooler and a stirrer was charged with 169.2 parts (1.8 mol) of phenol, 22 parts of resorcin (0.2 mol), and 4,4'-bismethoxy group. 207.7 parts (0.858 moles) of methylbiphenyl and 0.15 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 90.3 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 925 by GPC analysis, and the weight average molecular weight (Mw) was 1,180.

Example 9 is equipped with a thermometer and placed. 169.2 parts (1.8 mol) of phenol, 22 parts of resorcin (0.2 mol), 4,4'-bismethoxy group in a glass four-necked flask of 1000 outlets of a distillation outlet, a cooler and a stirrer. 312.3 parts (1.29 moles) of methylbiphenyl and 0.15 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 120 ° C to 135 ° C for 3.5 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 125.6 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 2044 and the weight average molecular weight (Mw) was 11306 by GPC analysis.

Example 10 is equipped with a thermometer and placed. 171.8 parts (1.83 mol) of phenol, 18.9 parts of resorcin (0.17 mol), 4,4'-bismethoxy 96.8 parts (0.4 moles) of methylbiphenyl and 0.05 parts of 50% by weight of sulfuric acid. The reaction was carried out under an internal temperature of 120 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 73.0 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 822 by GPC analysis, and the weight average molecular weight (Mw) was 957.

Example 11 is equipped with a thermometer and placed. 171.8 parts (1.83 mol) of phenol, 18.9 parts of resorcin (0.17 mol), 4,4'-bismethoxy 113.16 parts (0.4 moles) of chlorobiphenyl. The reaction was carried out under an internal temperature of 120 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 78.0 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 882 by GPC analysis, and the weight average molecular weight (Mw) was 1171.

Comparative Example 1 is equipped with a thermometer and placed. 10,000 parts of phenol (2 moles) and 112.6 parts of 4,4'-bismethoxymethylbiphenyl (0.465 moles) were added to a 1000-volume glass four-necked flask of a distillation outlet, a cooler and a stirrer. 50% by weight of sulfuric acid 0.09 parts. The reaction was carried out at an internal temperature of 110 ° C to 120 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 68 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 753 and the weight average molecular weight (Mw) was 896 by GPC analysis.

Comparative Example 2 is equipped with a thermometer and placed. 10,000 parts of phenol (2 moles) and 140.3 parts of 4,4'-bismethoxymethylbiphenyl (0.579 moles) were added to a 1000-volume glass four-necked flask of a distillation outlet, a cooler and a stirrer. 50% by weight of sulfuric acid 0.09 parts. The reaction was carried out under an internal temperature of 110 ° C to 120 ° C for 2.5 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, it was poured into pure water (250 parts) of 90 ° C or more and washed with water. The internal temperature was then raised to 160 ° C, and the unreacted components were removed under reduced pressure-steam treatment. A resin having a softening point of 74 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 915 by GPC analysis, and the weight average molecular weight (Mw) was 1191.

Comparative Example 3 is equipped with a thermometer and placed. Adding 405.8 parts (3.689 moles) of resorcinol and 207.7 parts of 4,4'-bismethoxymethylbiphenyl (0.858 Mo) to a 1000-volume glass four-necked flask of a distillation outlet, a cooler and a stirrer Ear) and 0.10 parts of 50% by weight sulfuric acid. The reaction was carried out at an internal temperature of 110 ° C to 140 ° C for 3 hours under nitrogen, and further at 165 ° C for 3 hours, and cooled to 95 ° C. After cooling, the internal temperature was raised to 160 ° C, and the unreacted components were removed under reduced pressure. A resin having a softening point of 95 ° C was obtained. The number average molecular weight (Mn) in terms of polystyrene was 891 by GPC analysis, and the weight average molecular weight (Mw) was 1038.

The analysis method of the resin and the hardener obtained by the present invention is as follows.

Novolak resin

(1) Gel permeation chromatography analysis: GPC determination method. Type: HLC-8220 Dongsuo (stock) company. Pipe column: TSK-GEL H type G2000H × L 4 pieces G3000H × L 1 branch G4000H × L 1 branch. Determination conditions: column pressure 13.5MPa. Solvent: tetrahydrofuran (THF). Flow rate: 1mL / min. Measuring temperature: 40 ° C. Detector: Spectrophotometer (UV-8020). Range: 2.56 wavelength 254nm & RI

(2) Softening point. The sample was melted, filled in a copper ring, and cooled to room temperature. . The ring filled with the sample is attached to an automatic softening point measuring device (type; EX-719PD Alex Scientific Co., Ltd. (ELEX SCIENTIFIC CO., Ltd.). Automatic softening point measuring device oil heating rate; 4 Starting at °C/min.. The oil bath temperature when the 3.5g steel ball passes through the sensor is taken as the softening point (the average of n=2)

(3) ICI viscosity. The disk temperature of the ICI cone disk viscometer is set to 150 °C. Select the cone for the sample viscosity. Place the sample in the center of the 150 °C hot plate and then contact the cone with it. Turn on the motor switch after 90 seconds and read the value at the point where the indicator value is stable. The average value of n=2 as the viscosity value

(4) Conductivity. The sample was accurately weighed to 8.0 ± 0.1 g in a 100 mL poly bottle, and 80 mL of ion-exchanged water having a conductivity of 2.0 μS/cm or less was placed in a graduated cylinder. . It was extracted at 95 ° C × 20 hours in a hot air circulation drier. . After 20 hours, it was taken out from the dryer, immersed in a low-temperature constant temperature water bath, and cooled at 25 °C. . The electrode of the solution conductivity meter (manufactured by Kyoto Electronics Co., Ltd.) was immersed in the extraction aqueous solution until the conductance value was stabilized. . The value of the stability point is taken as the conductivity.

(5) OH equivalent (summary: acetonitrile with ethyl chloroform, excess acetonitrile is decomposed by water, titrated with alkali). Precision scale sample 1g, add 1,4-two Alkane 10 mL was dissolved. . After confirming the dissolution, 10 mL of a 1.5 mol/L ethyl hydrazine chloride/anhydrous toluene solution was added, and the mixture was cooled to 0 °C. . 2 mL of pyridine was added, and the reaction was carried out for 1 hour in a water bath of 60 ± 1 °C. . After the reaction, the mixture was cooled, and 25 mL of pure water was added, and the mixture was thoroughly mixed to decompose acetonitrile. . Add acetone 25 mL, phenolphthalein. . It was titrated with 1 mol/L-potassium hydroxide until the sample solution was reddish purple. . For the blank group (no sample), the measurement was carried out in the same manner as above.

Calculated according to the following formula.

OH equivalent [g/eq.] = (1000 × W) / (f × (B - A)) Here, W: sample weight [g] f: 1 mol / L - potassium hydroxide factor = 1.002 B: titration 1 mol/L-potassium hydroxide used in the blank group [ml]A: 1 mol/L-potassium hydroxide used in the titration sample [ml]

hardener

(6) Determination of water absorption. It was molded at 150 ° C × 5 hours + 180 ° C × 3 hours to harden into the following dimensions. Dimensions: (Φ50 ± 1) × (3 ± 0.2) (diameter × thickness: mm). The surface was sufficiently wiped to measure the weight of the sample. . Put in a 100 mL sample bottle and add 80 mL of pure water. . Water absorption was carried out in a hot air circulation drier at 95 ° C for 24 hours. . After 24 hours, it was taken out from the dryer, immersed in a low-temperature constant temperature water bath, and cooled at 25 °C. . After cooling, the moisture adhering to the surface was sufficiently wiped, and the weight was measured. . According to the following formula, the water absorption rate is obtained.

Water absorption rate [%] = ((B-A) / A) × 100 A: Weight before water absorption [g] B: Weight after water absorption [g]

(7) Determination of glass translocation temperature (Tg). The hardened sample was cut into the following dimensions at 150 ° C × 5 hours + 180 ° C × 3 hours. Dimensions: (50 ± 1) × (40 ± 1) × (100 ± 1) (length × width × height: mm). Measuring device: The sample was attached to a TMA-60 (manufactured by SHIMADZU) measuring instrument and measured under nitrogen. . Temperature increase rate: The temperature was measured at a temperature increase rate of 3 ° C /min to 350 ° C, and the temperature at the turning point was measured as the glass transition temperature (Tg).

(8) Determination of mechanical properties of the hardened material (elasticity, energy, displacement, stress, deformation). The hardened sample was cut into the following dimensions at 150 ° C × 5 hours + 180 ° C × 3 hours. Dimensions: (75 ± 1) × (6 ± 1) × (4 ± 1) (length × width × height: mm). Measuring apparatus: autograph (type: AG-5000D manufactured by SHIMADZU Co., Ltd.), drop speed: 10 mm/min, distance between two points: 50 mm, and compression bending test was performed at room temperature.

The physical properties of the novolac resin synthesized according to the above Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Table 1.

Each of the novolak resins in Table 1 was used as a curing agent, and EOCN-1020-70 (epoxy equivalent: 197 g/eq) manufactured by Nippon Kayaku Co., Ltd. was used as an epoxy resin, and triphenylphosphine was used as a hardening agent. Promoter use. It is mixed with the above epoxy resin in the same equivalent ratio, heated at 150 ° C, melt-mixed, vacuum defoamed, and then molded at 150 ° C, and hardened at 150 ° C for 5 hours and 180 ° C for 3 hours to obtain epoxy resin hardening. Things. The blending and physical properties of the obtained epoxy resin cured product are shown in Table 2.

Each of the novolak resins in Table 1 was used as a curing agent, and Epikote YX-4000 (epoxy equivalent: 187 g/eq) manufactured by Nippon Epoxy Co., Ltd. was used as an epoxy resin, and three were used. Phenylphosphine is used as a hardening accelerator. It is mixed with the above epoxy resin in the same equivalent ratio, heated at 150 ° C, melt-mixed, vacuum defoamed, and then molded at 150 ° C, and hardened at 150 ° C for 5 hours and 180 ° C for 3 hours to obtain epoxy resin hardening. Things. The blending and physical properties of the obtained cured epoxy resin are shown in Table 3.

Stretched biphenyl crosslinker: 4,4'-bismethoxymethylbiphenyl (BMMB) 4,4'-dichloromethylbiphenyl (RCMB)

[Possibility of industrial use]

According to the present invention, it is possible to provide a low water absorption (low hygroscopicity), heat resistance, flame retardancy, mechanical properties, and adhesive properties, and the epoxy resin hardens faster than the prior art extended phenyl crosslinked novolac resin. Stretched biphenyl crosslinked novolac resin.

Further, the extended phenyl crosslinked novolak resin of the present invention can be used as an epoxy resin by reacting with epichlorohydrin, and can also be used as a flame retardant because it contains a stretched biphenyl crosslinking group.

Claims (7)

a phenyl crosslinked novolac resin represented by the following formula (2), Wherein R ¹ , R ² and R ³ may each be the same or different, and the plural R ¹ , R ² and R ³ may be the same or different, and represent a substituted or unsubstituted straight chain of 1 to 10 carbon atoms or a branched alkyl group, a substituted or unsubstituted aryl group, p1 and p3 represent an integer of 0 to 4, p2 represents an integer of 0 to 3, n represents an integer of 0 to 15, and m1, m2 and m3 each represent 1 or 2 The integer, the plural m2 may be the same or different, except that m1, m2, m3 are all 1 or all 2 except. The exfoliated phenyl crosslinked novolac resin according to the first aspect of the invention, wherein the exfoliated phenyl crosslinked novolac resin is a biphenyl compound represented by the following formula (1) and contains at least one dihydric phenol. a product obtained by reacting a phenolic mixture of components, which contains 100 to 80 moles of dihydric phenol in 100 moles. In the formula, X represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom. The extended phenyl crosslinked novolac resin of claim 2, wherein the phenolic mixture is used in an amount of from 1.2 to 5.5 moles per mole of the biphenyl compound. A hardener for epoxy resin, which is composed of a bisphenyl crosslinked novolac resin of the first application of the patent scope. An epoxidized varnish resin which is subjected to epoxidation by extending a phenyl crosslinked novolac resin of the first application of the patent scope. An epoxy resin composition comprising the extended biphenyl crosslinked novolac resin and epoxy resin of the first application of the patent scope. A cured product comprising the epoxy resin composition of claim 6 of the patent application.