WO2007026553A1

WO2007026553A1 - Low softening point phenol novolac resin, method for producing same, and epoxy resin cured product using same

Info

Publication number: WO2007026553A1
Application number: PCT/JP2006/316247
Authority: WO
Inventors: Seiichirou Takabayashi; Kumi Mitsumoto
Original assignee: Ube Industries, Ltd.
Priority date: 2005-08-31
Filing date: 2006-08-18
Publication date: 2007-03-08
Also published as: KR20080050454A; CN101233165A; TWI399392B; JP5136055B2; TW200720328A; JP2012167289A; KR101285422B1; JPWO2007026553A1; JP5413488B2; CN101233165B

Abstract

Disclosed is a low softening point phenol novolac resin characterized by having a constitutional unit represented by the general formulae (1) below and a melt viscosity at 150°C of 20-100 mPa·s. Also disclosed is a method for producing such a low softening point phenol novolac resin. In the formulae (1), R represents at least one divalent arylene group selected from a biphenylene group and a xylylene group represented by the following general formulae (2): and may further contain a constitutional unit represented by the following general formula (3): (wherein R4 represents a hydroxyl group or an alkyl group having 1-6 carbon atoms); m and n represent numbers satisfying m/n = 0.04-20; R1, R2 and R3 may be the same as or different from one another and respectively represent a hydroxyl group or an alkyl group having 1-6 carbon atoms; and p, q and r respectively represent an integer of 0-2.

Description

Specification

Low softening point phenol novolac resin, process for producing the same, and cured epoxy resin using the same

Technical field

[0001] The present invention relates to a low soft-point phenol novolak resin useful for various binders, coating materials, laminates, molding materials, and the like, a production method thereof, and an epoxy resin cured product using the same. Particularly suitable for epoxy resin hardeners for semiconductor encapsulation, printed circuit board insulation, etc., low melting viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, and flame resistance The present invention relates to a soft soft-point phenol novolac resin, a method for producing the same, and a cured epoxy resin using the same. Background art

[0002] Various phenolic polymers such as phenol novolac resin, phenol alcohol resin, etc. are used as epoxy resin hardeners for electronic materials, particularly for semiconductor encapsulation and printed circuit board insulation. In recent years, as semiconductor packages have become smaller and thinner, more pins, and higher-density packaging, higher performance resin has been demanded.

[0003] When used in a single-side sealed package such as a BGA (Ball Grid Array), it has an excellent performance that the warpage of the package is small. However, in recent semiconductor packages, for example, in the case of BGA, it has become a finer pitch and collective sealing type, and in addition to low warpage, it has high fluidity and good adhesion to the substrate surface. And so on. In addition, low melt viscosity improves fluidity and adhesion and is advantageous in terms of solder heat resistance and water resistance because a large amount of filler can be blended. In other words, in order to satisfy the required properties for these encapsulants, low soft-point phenol novolac resin that combines low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, and flame retardancy. The appearance of is strongly desired.

[0004] In addition, an epoxy resin composition having excellent water resistance and high adhesion at a high glass transition temperature is also desired for an interlayer insulating material for build-up substrates. A phenolic curing agent having excellent storage stability and having low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, and flame retardancy is desired. [0005] Epoxy resin is often used as a resin material for electronic materials, and various phenol novolak condensates, amines, and acid anhydrides are used as a hardener for the epoxy resin. In particular, as a curing agent for epoxy resin for semiconductor (IC) sealing, a phenolic nopolac condensate is mainly used from the viewpoint of heat resistance and reliability. In recent years, high integration of ICs, small size and thinning of the packaging, and the application of surface mounting methods have progressed, and the sealing material has thermal shock resistance and soldering heat resistance during surface mounting work. There is a demand for further improvement. A major factor affecting the soldering heat resistance is the hygroscopicity of the sealing resin material. In other words, the moisture-absorbing sealing material generates an internal pressure due to vaporization of water at a high temperature during the surface mounting operation, causing internal peeling and package cracks, resulting in poor soldering heat resistance. Therefore, the phenolic novolak condensate used as an epoxy resin hardener is particularly required to have low hygroscopicity.

[0006] As a method of reducing the hygroscopicity of the sealing material, there is a method of increasing the amount of filler such as non-hygroscopic silica filled in the sealing resin material as the filler. In this case, if the viscosity of the base resin material is high, the high filling property of the filler is impaired. Therefore, it is desirable that the phenolic nopolac condensate used as the curing agent has a low viscosity. In addition, the sealing material is required to have heat resistance, high strength, toughness, flame retardancy, adhesive strength, and the like. Conventional sealing resin materials that use phenol novolac condensates as curing agents for sealing epoxy resins are relatively high in hygroscopicity and are not sufficiently satisfactory in terms of other physical properties. I got it.

[0007] Therefore, various phenol novolak condensates have been proposed in order to improve hygroscopicity, heat resistance, adhesion, flame retardancy, and the like. For example, there are novolak condensates using alkylphenols such as o cresol, and novolak condensates using naphthols such as 1 naphthol (see, for example, Patent Documents 1 to 3). Also, a phenolic compound using di (hydroxypropyl) biphenyl as a phenol condensing agent has been disclosed (see Patent Document 4), and phenol using a bis (methoxymethyl) biphenyl mixture. A novolak condensate has been proposed (see Patent Document 5). Furthermore, an epoxy resin molding material for electronic component sealing that effectively uses formaldehyde (see Patent Document 6) is disclosed. However, materials with further improved hygroscopicity, heat resistance, adhesive properties, flame retardancy, etc. are desired. [0008] Patent Document 1: Japanese Patent Application Laid-Open No. 59-230017

Patent Document 2: Japanese Patent Laid-Open No. 05-0778437

Patent Document 3: Japanese Patent Laid-Open No. 05-086156

Patent Document 4: Japanese Patent Laid-Open No. 05-117350

Patent Document 5: Japanese Patent Laid-Open No. 08-143648

Patent Document 6: Japanese Patent Laid-Open No. 63-022284

Non-Patent Document 1: D. W. van Krevelen, Polymer, 16, 615 (1975)

Disclosure of the invention

Problems to be solved by the invention

The subject of the present invention is excellent in low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, flame retardancy, etc., especially for electrical and electronic industries, for sealing electronic parts , A novel phenol novolac resin suitably used for epoxy resin for laminated board materials, and an epoxidized phenol novolak condensate obtained by epoxidizing this phenol novolac resin and reacting it with a curing agent for epoxy resin It is in providing the obtained epoxy resin hardened | cured material.

[0010] However, if the introduction rate of the biphenyl group is increased in order to increase the OH equivalent to reduce moisture absorption, the melt viscosity increases. As a result, the fluidity is poor due to an increase in melt viscosity, causing molding problems. When the molecular weight is decreased to lower the melt viscosity, the glass transition temperature is lowered and the curability at the time of molding is lowered. That is, it is considered that it is difficult in principle to achieve both low hygroscopicity, low melt viscosity, curability and high glass transition temperature. Means for solving the problem

[0011] The present inventors have intensively studied to obtain a phenol-based curing agent having the low hygroscopicity, high adhesion, and heat-resistant physical properties of the phenol novolak resin having an aryl group-containing crosslinking group and having a low melt viscosity. As a result, by having both an alkylene-type polymer unit and a phenol'formaldehyde polymer unit in the cross-linking group in the molecule, and setting the ratio of the degree of polymerization of both in a specific range, low melt viscosity and low hygroscopicity, The present invention was completed by finding that a low soft spot phenolic novolac resin having high adhesion and heat resistance was obtained.

That is, the present invention provides the following general formula (1):

[0014] In the formula, R represents the following general formula (2)

The biphenol-xylene group and the xylylene group represented by formula (1) represent at least one divalent arylene group selected from the following general formula (3):

In the formula, R ⁴ may be a hydroxyl group or an alkyl group having 1 to 6 carbon atoms, and may include a structural unit represented by: m and n are numbers that satisfy mZn of 0.04 to 20 Preferably, m / n is 0.05 to 9, and

R ² and R ^{3, which} may be the same or different, are each a hydroxyl group or an alkyl group having 1 to 6 carbon atoms, and P, q, and r are each an integer of 0 to 2 ,

And having a melt viscosity at 150 ° C. of 20 to: L00 mPa ′s, preferably 25 to 90 mPa ′s.

[0015] The present invention also provides phenols, the following general formula (4):

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

The low softness represented by the above formula (1) is characterized in that at least one of the substituted biphenyl-reny compound and substituted benzene compound represented by formula (II) and formaldehyde are condensed in the presence of an acid catalyst. The present invention relates to a method for producing saddle point phenol novolac resin. In the production method of the present invention, in addition to the compound of the formula (4), the following general formula (5)

In the formula, R ⁴ has the same meaning as above.

It may contain a benzaldehyde compound represented by:

[0017] Further, the present invention relates to an epoxy resin cured product containing the low soft spot phenol novolac resin represented by the general formula (1). The invention's effect

[0018] The low soft low point phenol novolak resin of the present invention has both polymer units of the aryl group-containing cross-linked type resin and the methylene group cross-linked phenol novolak resin in the molecule. By adopting a structure in which the ratio of the degree of polymerization is in a specific range, low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, and flame resistance suitable for epoxy resin curing agents are achieved. It is a cohesive oil. This makes it compatible with the latest semiconductor encapsulation materials such as BGA and can be used as an epoxy resin hardener.

BEST MODE FOR CARRYING OUT THE INVENTION

[0019] The phenol novolac resin of the present invention is a polymerization unit of a phenol novolac resin containing n total methylene crosslinking units of a phenol novolac resin containing a phenol crosslinking group represented by the general formula (1) and a methylene crosslinking group. It is a copolymer type low softening point phenol novolac resin having a total of m, and there is no problem even if it is a block copolymer or a random copolymer. The degree of polymerization of mZn is 0.04 to 20, preferably ί or 0.05 to 9, more preferably ί or 0.09 to 6, most preferably ί or 0.1 to 2, and 150 °. A resin having a melt viscosity in C of 20 to: L00 mPa's, preferably 25 to 98 mPa's. Even when the above structural unit (3) is not included, the m / n value of the degree of polymerization of each polymerization unit ^ 0.04 to 20, preferably ί or 0.05 to 9, more preferably ί or 0.00. 09 to 6, most preferably 0.1 to 2 and the melt viscosity at 150 ° C is 20 to: more preferably LOOmPa's, more preferably 25 to 98 mPa's, more preferably 30 to 95mPa's. In the low soft spot phenol novolac resin of the present invention, when mZn exceeds 20, the glass transition temperature is lowered, and further, the flame retardancy tends to be reduced, which is not preferable. On the other hand, if mZn is less than 0.04, the melt viscosity increases and the fluidity deteriorates, which is preferable.

[0021] phenols used in the present invention, as described in the general formula (1), having at least one hydro hexyl group on the benzene ring, optionally substituted with R \ R ² or R ³ phenol It is kind. Here, R ¹ R ² and R ³ may be the same or different, and a plurality of R ¹ R ² and R ³ may be the same or different, respectively. 1 to 6 alkyl groups, and p, q and r are each a substituent group consisting of an integer of 0 to 2. Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. Including body.

These phenols can be used alone or in admixture of two or more. Specific phenols include, for example, 0 to 2 carbon atoms such as phenol, cresol, ethyl phenol, propino enoenole, butino enoenole, hexeno enoenore, xylenenole, butino methenophenol, etc. In addition to monovalent phenol substituted with 6 alkyl groups, divalent phenol substituted with 2 hydroxyl groups such as catechol, resorcin, hydroquinone and the like.

[0022] The compound that forms a methylene crosslinking group in the present invention is preferably formaldehyde. Further, the form of formaldehyde is not particularly limited, and a formaldehyde aqueous solution and a polymer that decomposes in the presence of an acid such as paraformaldehyde and trioxane to formaldehyde can also be used.

Preferred is an aqueous formaldehyde solution that is easy to handle, and a commercially available 42% aqueous formaldehyde solution can be used as it is.

[0023] The aryl group-containing crosslinking group R used in the present invention includes a divalent arylene group represented by the general formulas (2) and (3).

Such divalent arylene groups include, for example, 4, 4, bibiphenylene, 3, 3, 1 biphenylylene, 2, 2, 1 biphenylylene, 2, 4, 1 biphenylylene. Group, 1,4-xylylene group, 1,3-xylylene group, 1,2-xylylene group and the like. Among these, In the present invention, a 4,4, bibi-rylene group and a 1,4 xylylene group are particularly preferred. Specific examples of the aryl group-containing crosslinking group-forming compound for leading to the substituent include, for example, the above general formula ( Examples thereof include compounds represented by 4) and (5).

In the general formulas (4) and (5), X is a halogen atom, a hydroxyl group or an alkoxyl group having 1 to 6 carbon atoms, and R ⁴ is a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. is there. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Examples of the alkoxyl group include linear or branched alkoxyl groups having 1 to 6 carbon atoms such as methoxyl group, ethoxyl group, propoxyl group, butoxyl group, pentyloxyl group, hexyloxyl group, and the like. Also includes various isomers. Examples of the alkyl group include those described above.

Specific compounds for leading to the above substituents include, for example, 4,4'-di (methoxymethyl) biphenyl, 2,2, -di (methoxymethyl) biphenyl, 2,4, di Di (alkoxymethyl) biphenyl compounds such as (methoxymethyl) biphenyl, 4.4, -di (chloromethyl) biphenyl, 2,2, -di (chloromethyl) biphenyl, 2, Di (Noguchigenomethyl) biphenyl compounds such as 4, -di (chloromethyl) biphenyl, 4, 4, -di (hydroxymethyl) biphenyl, 2, 2'-di (hydroxymethyl) biphenyl Di (hydroxymethyl) biphenyl compounds such as 2,4'-di (hydroxymethyl) biphenyl, 1,4-di (methoxymethyl) benzene, 1,3 di (methoxymethyl) benzene, Di (alkoxymethyl) benzene compounds such as 2-di (methoxymethyl) benzene, 1,4 di Chloromethyl) benzene, 1,3 di (chloromethyl) benzene, 1,2-di (chloromethyl) benzene and other di (no-necked genomethyl) benzene compounds, 1,4-di (hydroxymethyl) benzene, 1, 3 Di (hydroxymethyl) benzene, 1, 2— Di (hydroxymethyl) benzene compounds such as di (hydroxymethyl) benzene, benzaldehyde, 2 hydroxybenzaldehyde, 3 hydroxybenzaldehyde, 4-hydroxybenzaldehyde compounds such as 4-hydroxybenzaldehyde, 2— Examples thereof include alkylbenzaldehyde compounds such as methylbenzaldehyde, 3-methylbenzaldehyde, and 4-methylbenzaldehyde. These isomers can be used alone or as a mixture, preferably when used as a mixture of different isomers.

More preferably, it is an isomer mixture of a biphenol-renylene compound and a Z or xylylene compound.

In the mixture of isomers of Bihue-Rylene compound and Z or Xylylene compound, the power is most preferable when 1,4 and 4,4 ′ monomers contain at least 50 mol%.

However, in the case of using as a mixture, the mixture ratio is 4, 4'Bifueniriren groups 20 to 50 mol ^_0/0 relative to 1 mol 1, 4 is preferable to use a xylylene group.

[0024] [Method for producing low soft saddle point phenol novolac resin]

[0026] The method for producing a low softening point phenol novolak resin represented by the general formula (1) is capable of forming n-fold moles of R, ie, an aryl group-containing crosslinking group, with respect to a certain amount of phenols in the presence of an acid catalyst. It can be carried out in a single-stage condensation reaction by simultaneously adding the compound for use and m-fold mol of formaldehyde.

In this case, the total amount of the aryl group-containing crosslinking group-forming compound and formaldehyde is preferably 1 mol, preferably 2 to 10 mol, more preferably 3 to 6 mol, and even more preferably 4 mol or more of phenols. When used, the reaction between phenols and formaldehyde is preferentially performed at a low reaction temperature (for example, around 100 ° C) to mainly form a phenolic novolac resin containing a low molecular weight methylene crosslinking group, Next, it is preferable to employ a system in which the temperature is increased or the catalyst is increased to react the methylene crosslinking group-containing phenol novolak resin, the arylene-containing crosslinking group-forming compound, and the phenols.

The acid catalyst to be used is not particularly limited, and known acids such as hydrochloric acid, succinic acid, sulfuric acid, phosphoric acid and the like, and organic acids such as paratoluenesulfonic acid may be used alone or in combination of two or more. Particularly preferred is sulfuric acid, succinic acid or paratoluenesulfonic acid. The temperature of the condensation reaction is 50 to 120 ° C, preferably 80 to 110 ° C as a low temperature condition. The reaction temperature at the time of raising the temperature is 130 to 230 ° C, preferably 150 to 200 ° C.

The time for the condensation reaction varies depending on the reaction temperature and the type and amount of catalyst used.

About 1 to 24 hours.

The reaction pressure is usually carried out under normal pressure, but there is no problem even if it is carried out under a slight pressure or reduced pressure.

If the amount of phenol used is less than 2 moles per mole of total aryl group-containing crosslinking group-forming compound and formaldehyde, such as when the molecular weight is high, the melt viscosity is high. In some cases, phenol novolac resin cannot be obtained.

Therefore, the low soft-point phenol novolac resin of the present invention condenses phenols and formaldehyde in the presence of an acid catalyst in advance, and then condenses by adding an R aryl group-containing cross-linking group forming compound. It can also be produced by a two-stage condensation reaction. In such a two-stage condensation reaction, phenols can be newly added in the second-stage reaction, and it is preferable to use excessive phenols in this case as well as in the first-stage reaction. Yes. For example, in the first stage reaction, phenols are present in an amount of 2.5 moles or more, more preferably 3.3 to 10 moles per mole of formaldehyde, and an aryl group-containing cross-linking group is added in the second stage reaction. The total amount of phenols to be fed in 1 to 2 stages is 3 moles or more, compared to 1 mole in total of the aryl group-containing cross-linking group forming compound and formaldehyde that is charged in a total of 1 to 2 stages of reaction. More preferably, it is important to use in the range of 3.3 to 10 moles.

When such a two-stage condensation reaction is performed, the degree of polymerization of each polymer unit of the aryl group-containing cross-linking group type phenol novolak resin and the methylene cross-linking group-containing phenol novolac resin, that is, the distribution of n and m becomes narrow, It is preferable for the purpose of the present invention because the molecular weight can be easily controlled and a polymer having a desired melt viscosity can be easily obtained.

An example of a two-stage condensation reaction is shown in the following reaction formula.

(A)

[0030] The two-stage condensation reaction can be carried out according to the one-stage condensation reaction conditions.

The amount of the acid catalyst used in the first-stage condensation reaction and the second-stage condensation reaction varies depending on the type, but in the case of oxalic acid, 0.1 to 2.0% by mass with respect to the phenols used. In the case of sulfuric acid, it is preferable to use about 0.05 to 0.5% by mass, and in the case of paratoluenesulfonic acid, about 0.02 to 0.1% by mass. In particular, when a two-stage condensation reaction is performed, sulfuric acid or para-toluenesulfonic acid may be used when the second-stage aryl group-containing crosslinking group is reacted with phenols and methylene crosslinking group phenol novolac resin. I like it. The reaction temperature is not particularly limited, but is preferably set in the range of about 60 to 160 ° C. More preferably, it is 80-140 degreeC.

[0031] After the condensation reaction in the presence of an acid catalyst, the unreacted phenols and the acid catalyst are removed, whereby the low soft spot phenol novolac resin of the present invention can be obtained. The method for removing phenols is generally a method in which heat is applied under reduced pressure or while blowing an inert gas to distill the phenols out of the system. The acid catalyst can be removed by a method such as washing with water.

[0032] In the method for producing the low soft point phenol novolak resin of the present invention, the amounts of raw material phenols, arylene-containing crosslinking group forming compounds and formaldehyde are controlled, and By setting the reaction conditions as described above, a resin having a desired melt viscosity at 150 ° C. can be obtained.

[0033] The low soft-point phenol novolak resin of the present invention is characterized by the polymerization units of the aryl group-crosslinked phenol novolac resin and the methylene-crosslinked phenol novolak resin in the molecule. It is a structure having both at a fixed ratio, and is suitable as a raw material for epoxy resin having low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, and flame retardancy.

[0034] Further, the low soft-point phenol novolak resin of the present invention can be widely used for applications such as binders, coating materials, laminated materials, molding materials, etc., but particularly has a low melt viscosity and a high glass transition temperature. Since it has low hygroscopicity, high adhesion, heat resistance, and flame retardancy, it is particularly suitable for epoxy curing agents for semiconductor encapsulation and printed circuit board insulation.

[0035] [Epoxy resin hardened product]

The low soft spot phenol novolac resin of the present invention can be used as a curing agent for epoxy resin as an example. The cured epoxy resin can be obtained by mixing a phenolic polymer, an epoxy resin and a curing accelerator and curing them in a temperature range of 100 to 250 ° C.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, triphenol methane type epoxy resin, Glycidyl ether type epoxy resin such as biphenol-epoxy type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, halogenated epoxy resin, etc. have two or more epoxy groups in the molecule. And epoxy resin. These epoxy resins may be used alone or in combination of two or more.

[0037] (Curing accelerator)

As the curing accelerator, a known curing accelerator for curing epoxy resin with a phenolic curing agent can be used. Examples of such curing accelerators include organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and their tetraphenylpolone salts. From the viewpoint of curability and moisture resistance, triphenylphosphine and 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) are preferred. In order to achieve higher fluidity, tetraphenol phosphor derivatives such as tetraphenyl phosphate and tetraphenyl phosphate are preferred, which are heat-latent curing accelerators that exhibit activity when heated. preferable.

[0038] (Other additives) In the epoxy resin composition of the present invention, an inorganic filler, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance as necessary. In particular, when used for semiconductor encapsulation, it is essential to add inorganic fillers. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum. Calcium carbonate, magnesite, clay, talc, my strength, magnesia, barium sulfate, etc. are preferable, but amorphous silica, crystalline silica, etc. are particularly preferable. It may be the same as the amount used in the epoxy resin composition for semiconductor encapsulation.

[0039] The alkyl type resin of the present invention has an appropriate amount of phenol novolac resin unit, and when used as an epoxy resin hardener, has a high glass transition temperature, low moisture absorption, high adhesion, heat resistance, In addition, the flame retardancy can be maintained and the viscosity can be reduced.

Example

[0040] The present invention will be specifically described below with reference to examples. In addition, the evaluation method of the phenol novolak rosin obtained by this invention is shown.

[0041] (l) Measurement of ICI viscosity

ICI cone plate viscometer: MODEL CV—IS manufactured by TOA Kogyo Co., Ltd. was used. Set the ICI viscometer plate temperature to 150 ° C and weigh approximately 0.04 g of the sample. Place the weighed grease on the plate, press it with a cone from the top, and leave it for 90 seconds. Rotate the cone and read its torque value as ICI viscosity.

(2) Measurement of gel time

Add epoxy resin and phenol resin to the test tube so that the equivalent of 1: 1, and weigh T pp to 0.1 wt% with respect to the epoxy and add to the test tube.

Place the test tube on a gel timer (Toshiba hour meter SFO-304M) with the oil temperature set at 150 ° C, and stir at one rotation per second using a SUS stir bar.

At first, the viscosity is low and it is liquid, but after a certain period of time, the viscosity of the resin increases rapidly and becomes a gel. The time spent during this period is defined as gel time.

The shorter this time is, the better the curability is!

[0042] Phenolic novolak sachets (Examples and Comparative Examples) synthesized under the conditions shown in Table 1 were hardened. When used as a softener, the epoxy resin is epoxidized bi-phenol novolac resin of NC-3000 (softening point 60 ° C, epoxy equivalent 270 g / eq) manufactured by Nippon Yakuhin Co., Ltd. Triphenylphosphine (sometimes abbreviated as TPP) was used as a curing accelerator. The low-soft-point phenol novolak resin of the present invention and the above epoxy resin are blended so that the phenol hydroxyl equivalent ratio and the epoxy equivalent ratio are 1: 1, and the TPP catalyst contains the epoxy resin weight of the blend. ^% Charged. These are melt-mixed by heating to 150 ° C, vacuum degassed, cast into a 150 ° C mold (thickness 4 mm), cured at 150 ° C for 3 hours, and then further 180 ° C. Cured over 5 hours to make a molded product.

The test methods for various physical properties of the obtained molded product (cured product) are as follows.

(3) Tg: TMA method (Thermal Mechanical Analysis) (heating rate 5 ° CZ min)

(4) Water absorption rate: 24 hours boiling method,

(5) Residual coal rate

Residual carbon and the oxygen index are in a proportional relationship, and it is generally said that a highly flame-retardant resin has a high residual carbon ratio (see Non-Patent Document 1). Therefore, it was measured as an index of flame retardancy. (Measuring method)

The molded body cured with the above composition is cut into 1.5 cm squares and weighed.

Place the cut sample in a crucible and reduce and bake in an electric furnace at 800 ° C for 60 minutes.

After cooling, the sample is weighed.

In addition, incinerate for 2 hours in an electric furnace at 800 ° C and measure the weight.

Obtain the remaining charcoal rate (%) from the following formula.

Residual carbon ratio (%) = (weight after calcination weight after ashing) Z sample weight X 100

Example 1

In a glass reaction kettle equipped with a stirrer, condenser, and nitrogen gas inlet tube, 376 g (4.0 mol) of phenol, 4, 4, dimethoxymethyl biphenyl (4, 4, BMMB) is abbreviated. ) 226 g (0.95), 42% formalin aqueous solution 3.6 g (0.05 mol), 50% sulfuric acid aqueous solution 0.22 g were charged and reacted at 100 ° C. for 1 hour.

Thereafter, the reaction was carried out for 3.5 hours while maintaining the reaction temperature at 165 ° C. During that time, the generated Tanol was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 340 g of phenol monovolak resin (150 ° C melt viscosity: 90 mPa · s).

Table 1 shows the physical properties of the molded novolac resin obtained by the above method.

Examples 2-12 and Comparative Examples 1-5

According to the method described in Example 1 except that the monomer composition shown in Table 1 was used, phenol nopolac rosin was obtained. The physical properties of each cured product are also shown in Table 1.

() ^ i 簦 [] t w0046lICIQ

4, 4 'ΒΜΜΒ: 4, 4'-di (methoxymethyl) biphenyl

4, 4 'BCBC: 4, 4'-di (chloromethyl) biphenyl

1, 4 PXDM: 1, 4-di (methoxymethyl) benzene

* 〔U0045 ICI cone plate viscometer: MODEL CV—IS manufactured by TOA Kogyo Co., Ltd. was used.

Set the ICI viscometer plate temperature to 150 ° C and weigh approximately 0.04 g of the sample. Place the weighed grease on the plate, press it with a cone from the top, and leave it for 90 seconds. Rotate the cone and read its torque value as ICI viscosity.

[0047] When phenol novolac resin (Examples and Comparative Examples) synthesized under the conditions shown in Table 2 was used as a hardener, the epoxy resin used was NC-3000 manufactured by Nippon Gyaku Co., Ltd. An epoxidized biphenyl novolac resin (softening point 60 ° C., epoxy equivalent 270 g / eq), and triphenylphosphine (sometimes abbreviated as TPP) was used as a curing accelerator. The low soft spot phenol resin of the present invention and the above epoxy novolac resin are blended so that the phenol hydroxyl group equivalent ratio and the epoxy equivalent ratio are 1: 1, and the TPP catalyst contains the epoxy resin weight of the blend. ^% Charged. These are melt-mixed by heating to 150 ° C, vacuum degassed, cast into a 150 ° C mold (thickness 4 mm), cured at 150 ° C for 3 hours, and then further 180 ° C. Cured over 5 hours to make a molded product.

(2) Tg: TMA method (Thermal Mechanical Analysis) (heating rate 5 ° CZ min)

(3) Water absorption rate: 24-hour boiling method,

[0048] Example 13

Into a glass reaction kettle equipped with a stirrer, condenser and nitrogen gas inlet tube, 376 g (4.0 mol) of phenol, 4, 4, di- (methoxymethyl) biphenyl (hereinafter 4, 4, — Abbreviated as BMMB.) 143 g (0.60 mol), 2,4, -di (methoxymethyl) biphenyl (abbreviated as 2, 4, — B MMB) 36 g (0.15 mol), 2. 2, -di (methoxymethyl) biphenyl (abbreviated as 2, 2, — BMMB) 48 g (0.20 mol), 42% formalin aqueous solution 3.6 g (0.05 mol), 50% sulfuric acid aqueous solution 0 22 g was charged and reacted at 100 ° C for 1 hour.

Thereafter, the reaction was further continued for 3.5 hours while maintaining the reaction temperature at 165 ° C. Meanwhile, the methanol formed was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 335 g of phenol novolac resin (150 ° C melt viscosity: 29 mPa · s). Table 1 shows the physical properties of the cured product obtained by the above method using the resulting phenol novolac resin.

[0049] Examples 14 to 18 and Comparative Examples 6 to 9

Phenolic novolac resin was synthesized according to the method described in Example 13, except that each monomer was used in the component ratio shown in Table 2. Further, a cured epoxy resin was obtained. Each physical property is shown together in Table 2.

[0050] * ₂

4,4'-ΒΜΜΒ: 4,4'-di (methoxymethyl) biphenyl

2,4'-ΒΜΜΒ: 2,4'-di (methoxymethyl) biphenyl

2, 2. '-ΒΜΜΒ: 2, 2'-di (methoxymethyl) biphenyl

4,4'-BCMB: 4,4'—Di (chloromethinole) biphenyl

2, 4 '-BCMB: 2, A'—Di (chloromethyl) biphenyl

2, 2 '-BCMB: 2, 2'-di (chloromethyl) biphenyl

1, 4-— PXDM: 1, 4--di (methoxymethyl) benzene

1, 2-PXDM: 1,2-Di (methoxymethyl) benzene

1, 3-PXDM: 1,3-Di (methoxymethyl) benzene

1, 4— PXDC: 1, 4-Di (chloromethyl) benzene

1, -PXDC: 1,2-Di (chloromethyl) benzene

1, 3-PXDC: 1,3-Di (chloromethyl) benzene

2-— HBA: 2--hydroxybenzaldehyde

3-HBA: 3-Hydroxybenzaldehyde As is clear from Table 2, the phenol novolac rosin obtained in Examples 13 to 18 and the cured product containing the aliphatic balun all have low melt viscosity, high glass transition temperature, and low hygroscopicity. However, in Comparative Examples 6 to 9, the physical property values of the deviations are reduced. Industrial applicability

[0052] According to the present invention, it is excellent in low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, flame retardancy, etc., especially for electrical and electronic industries, for sealing electronic components. A novel phenol novolak resin suitably used as an epoxy resin for laminated board materials, an epoxidized phenol novolak condensate obtained by epoxidizing this phenol novolac resin, and a reaction with a curing agent for epoxy resin. The obtained epoxy resin cured product can be provided. In addition, phenol novolac resin containing biphenol-rylene groups can be used as a flame retardant.

Claims

The scope of the claims

The following general formula (1):

In the formula, R is the following general formula (2)

In the formula, R ⁴ may be a hydroxyl group or an alkyl group having 1 to 6 carbon atoms, and may include a structural unit represented by: m and n are numbers that satisfy mZn of 0.04 to 20 Yes, and

R ² and R ^{3, which} may be the same or different, are each a hydroxyl group or an alkyl group having 1 to 6 carbon atoms, and p, q, and r are each an integer of 0-2. ,

A low-soft-point phenol novolak resin having a structural unit represented by the formula (1) and having a melt viscosity at 150 ° C of 20 to 1 OOmPa · s.

[2] The low soft-point phenol novolac resin according to claim 1, wherein R contains at least a 4,4′-biphenol-rylene crosslinking group.

[3] The low soft-point phenol novolak resin according to claim 2, wherein the biphenylylene cross-linking group is a mixture of isomers.

[4] The low-soft saddle point phenol novolak lunar effect according to claim 1, wherein mZn is a number satisfying 0.05 to 9. 2. The low soft spot phenol nopolac resin according to claim 1, which has a melt viscosity of 25 to 90 mPa's.

Phenols, following general formula (4):

X ₂ C ^ r- / = ^ CH ₂ X XH, C ^ = ^ CH ₂ X

, (Wherein X represents a halogen atom, a hydroxyl group or an alkoxyl group having 1 to 6 carbon atoms,

6. The method according to claim 1, wherein at least one of a substituted biphenyl-reny compound and a substituted benzene compound represented by formula (II) and formaldehyde are condensed in the presence of an acid catalyst. A method for producing the described low soft spot phenol novolac resin.

Furthermore, in addition to the compound of the formula (4), the following general formula (5):

In the formula, R ⁴ has the same meaning as above.

The method for producing a low soft-point phenol novolak resin according to claim 6, comprising a benzaldehyde compound represented by the formula:

(1) With respect to the total number of moles of cross-linking groups and formaldehyde constituting R,

(2) More than 3 moles of phenol,

8. The method for producing a low soft spot phenol novolak resin according to claim 6 or 7, further comprising a condensation step.

9. The low softness-point phenol monovolak according to claim 8, wherein the acid catalyst is a compound selected from the group forces of sulfuric acid, hydrochloric acid, oxalic acid, and paratoluenesulfonic acid. Manufacturing method of resin.

The low soft spot phenol novolac resin according to any one of claims 1 to 5 and the low obtained by the production method according to any one of claims 6 to 9. Hardened product containing at least one resin component selected from the group consisting of softening point phenol novolac resin An epoxy resin cured product obtained by reacting the cured product according to claim 10 with an epoxy resin.