CN101233165B

CN101233165B - Low softening point novolac resin, method for producing the same, and cured epoxy resin using the same

Info

Publication number: CN101233165B
Application number: CN2006800278970A
Authority: CN
Inventors: 高林诚一郎; 光本久未
Original assignee: Ube Industries Ltd
Current assignee: Ube Corp
Priority date: 2005-08-31
Filing date: 2006-08-18
Publication date: 2011-08-31
Anticipated expiration: 2026-08-18
Also published as: JP2012167289A; KR101285422B1; TWI399392B; JP5413488B2; TW200720328A; WO2007026553A1; JP5136055B2; JPWO2007026553A1; CN101233165A; KR20080050454A

Abstract

The present invention provides a low softening point phenol-formaldehyde novolac resin and a manufacturing method thereof, wherein the phenol-formaldehyde novolac resin is characterized in that: contains a structural unit represented by the following general formula (1),wherein R represents at least one 2-valent arylene group selected from biphenylene and xylylene groups represented by the following general formula ,

may further contain a structural unit represented by the following general formula (3)In the formula R⁴Is a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. Wherein m and n are numbers satisfying m/n of 0.04 to 20; and R is¹、R²And R³May be the same or different, and each is a hydroxyl group or an alkyl group having 1 to 6 carbon atoms; p, q and r are each an integer of 0 to 2. The novolak resin has a melt viscosity of 20 to 100 mPas at 150 ℃.

Description

Low softening point phenol novolac resin and manufacture method thereof and the epoxy resin cured product that uses it

Technical field

The present invention relates to low softening point phenol novolac (Phenol novolac) resin, its manufacture method useful in various tackiness agents, coating agent, stacking material, formed material etc. and use the epoxy resin cured product of this phenolic novolac.Especially relevant for being suitable for the epoxy curing agent that the insulation of semiconductor-sealing-purpose, printed base plate is used etc., have both low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance, and low softening point phenol novolac resin, its manufacture method of flame retardant resistance and use the epoxy resin cured product of this phenolic novolac.

Background technology

As being used for the epoxy curing agent that the insulation of electronic material, particularly semiconductor-sealing-purpose, printed base plate is used etc., for example can use various phenol polymers such as novolac-type resin, phenol alkyl resin.Yet in recent years, be accompanied by small-sized/slimming, many pinizations, the high density packingization of semiconductor packages, need the higher resin of performance.

When being used for the encapsulation of BGA single faces such as (Ball Grid Array), has the little excellent properties of warpage of packaging assembly.But nearest semiconductor packages further becomes pitchization or encapsulation type together for example under the situation of BGA, except reducing warpage, also require high workability and with the good adherence of substrate surface.Again,, a lot of fillers be can cooperate, thermotolerance and water tolerance aspect therefore also helped welding if low then flowability of melt viscosity or adherence improve.That is, for satisfying the characteristic to the requirement of these packaged materials, low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance, and the low softening point novolac resin of flame retardant resistance can appear having both in strong hope.

In addition, for the interlayer dielectic that increases laminar substrate, also the good composition epoxy resin of water tolerance excellence, high glass transition temperature and cementability appears in expectation, for realizing this target, it is solidifying agent with regard to the phenol with excellent in water resistance or preservation stability originally that expectation occurs, and it has both low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance, reaches flame retardant resistance.

Electronic material with using Resins, epoxy in the resin material more, and available various novolak condensess, amine, acid anhydrides are as this curing agent for epoxy resin.For the solidifying agent of semi-conductor (IC) encapsulating epoxy resin, consider from thermotolerance, reliability aspect, mainly use phenol varnish condenses.In recent years, small-sized, the slimming of highly integrated, the encapsulation of IC and the application of surface mounting mode are growing, and the requirement of the welding thermotolerance (Soldering Heat Resistance) to this encapsulation during with the resistance to sudden heating of material and surface mounting operation also further improves.As the stable on heating principal element of control welding, can be enumerated as the water absorbability of encapsulation with resin material.Also promptly, the encapsulation of moisture absorption can produce internal pressure because of the gasification of moisture with under the high temperature of material when the surface mounting operation, produces inside and peels off or encapsulate crackle and make welding thermotolerance variation.Therefore, special requirement are agent of low hygroscopicity as the phenol varnish condenses that epoxy curing agent uses.

As reducing the hygroscopic method of encapsulation with material, have be filled into encapsulation with in the resin material as the method for the packing material increment of the non-hygroscopic silicon-dioxide of packing material etc.At this moment, because if the viscosity height of base resin material, then the high fillibility of packing material is impaired, the viscosity of therefore wishing to be used as the phenol varnish condenses that solidifying agent uses is low.Again, encapsulation with material be required to have thermotolerance, high strength, obdurability, flame retardant resistance, bonding strength etc.Use in the past the encapsulation resin material of novolak condenses as the solidifying agent of encapsulating epoxy resin, its water absorbability is higher, and also can't fully meet the demands from other rerum natura aspect.

At this, various novolak condensess are proposed for making raisings such as water absorbability, thermotolerance, cementability, flame retardant resistance.Novolak (novolac) condenses that uses induced by alkyl hydroxybenzene such as ortho-cresol is for example arranged or use the novolak condenses (for example with reference to patent documentation 1 to 3) of aphthols such as 1-naphthols.Again, disclose and used the phenoloid (with reference to patent documentation 4) of two (hydroxypropyl) biphenyl, also disclose the novolak condenses (with reference to patent documentation 5) that uses two (methoxyl methyl) diphenyl mixtures in addition as the condensing agent of phenol.In addition, the electronic unit encapsulating epoxy resin formed material (with reference to patent documentation 6) that effectively utilizes formaldehyde is disclosed.Yet the material that water absorbability, thermotolerance, adhesion properties, flame retardant resistance etc. further improve appears in expectation.

Patent documentation 1: Japanese kokai publication sho 59-230017 communique

Patent documentation 2: Japanese kokai publication hei 05-078437 communique

Patent documentation 3: Japanese kokai publication hei 05-086156 communique

Patent documentation 4: Japanese kokai publication hei 05-117350 communique

Patent documentation 5: Japanese kokai publication hei 08-143648 communique

Patent documentation 6: Japanese kokai publication sho 63-022824 communique

Non-patent literature: D.W.van Krevelen, Polymer, 16,615 (1975)

Summary of the invention

Problem of the present invention is to provide a kind of have low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, excellent such as thermotolerance and flame retardant resistance, especially be suitable as the novel phenolic novolac of the Resins, epoxy use that electric industry and electronic industry are used, packaging of electronic parts is used, stacking panel material is used, and with this phenolic novolac epoxidation novolak condenses of forming of epoxidation in addition, and with its with the hardener for epoxy resin reaction epoxy resin cured product of acquisition.

But when improving the importing rate of xenyl for low moisture absorption turns to raising OH equivalent, melt viscosity can rise.The result causes the puzzlement in the shaping because of the rising of melt viscosity makes mobile variation for this reason.When dwindling molecular weight for reducing melt viscosity, second-order transition temperature descends, and the solidified nature during shaping can reduce.Also promptly, setting up in the time of agent of low hygroscopicity, low melting viscosity, solidified nature and high glass transition temperature, is difficulty to some extent on principle.

Present inventors etc. are for can apply flexibly above-mentioned the have agent of low hygroscopicity of the phenolic novolac of the crosslinking group that contains aryl, high adherence, thermotolerance rerum natura, and for the phenol that obtains low melting viscosity is that solidifying agent is concentrated on studies, found that and in intramolecular crosslinking group, have alkylene fundamental mode polymer unit and phenol yuban unit simultaneously, be maintained in the specified range by the ratio of the polymerization degree both, can obtain the low softening point phenol novolac resin of low melting viscosity and agent of low hygroscopicity, high adherence, excellent heat resistance, thereby finish the present invention.

Also promptly the present invention relates to a kind of low softening point phenol novolac resin, this phenolic novolac contains the structural unit shown in the following general formula (1),

In the formula, at least a divalent base of selecting in the base that R represents to be represented by following general formula (2):

Also can contain the structural unit shown in the following general formula (3),

In the formula, R ⁴Be the alkyl of hydroxyl or carbonatoms 1 to 6,

Wherein m and n are that to satisfy m/n be 0.04 to 20 number, and preferred m/n is 0.05 to 9, in addition R ¹, R ²And R ³Can be identical also can be different, respectively do for oneself 0 to 2 integer of the alkyl of respectively do for oneself hydroxyl or carbonatoms 1 to 6, p, q and r,

And this phenolic novolac is 20 to 100mPas at 150 ℃ melt viscosity, with 25 to 90mPaS for better.

Again, the present invention relates to a kind of manufacture method of low softening point phenol novolac resin, it is characterized by: in the presence of acid catalyst, make phenols, be selected from replacement Biphenylene compounds shown in following general formula (4) and at least a material and the formaldehyde condensation in the substituted benzene compound

In the formula, X represents the alkoxyl group of halogen atom, hydroxyl or carbonatoms 1 to 6.

In the manufacture method of the present invention, except the compound of above-mentioned formula (4), also can contain with the benzaldehyde compound shown in the following general formula (5):

In the formula, R ⁴With above-mentioned synonym.

Moreover, the present invention relates to a kind of epoxy resin cured product, it contains the low softening point phenol novolac resin shown in above-mentioned general formula (1).

Low softening point phenol novolac resin of the present invention, have the crosslinked fundamental mode resin that contains aryl and the polymerized unit of methylene-crosslinked phenolic novolac simultaneously at intramolecularly, and the ratio of both polymerization degree and both polymerization degree is in specified range, by adopting such structure, can obtain to be applicable to the resin of epoxy curing agent, this resin has both low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance and flame retardant resistance.Can tackle up-to-date semiconductor sealing materials such as BGA thus, can be used as epoxy curing agent and be used.

Embodiment

Phenolic novolac of the present invention, be n altogether of polymerized unit with the phenolic novolac that contains the aryl crosslinking group shown in above-mentioned general formula (1), the polymerized unit copoly type low softening point phenol novolac resin of m altogether that contains the phenolic novolac of methylene-crosslinked base, it also can be segmented copolymer or random copolymers, the m/n value of the polymerization degree of each polymerized unit is 0.04 to 20 in general formula (1), with 0.05 to 9 is preferable, again with 0.09 to 6 for better, with 0.1 to 2 is the best, and at 150 ℃ melt viscosities is 20 to 100mPas, with 25 to 98mPas for better.Again, even when not comprising said structure unit (3), the m/n value of the polymerization degree of its each polymerized unit is 0.04 to 20, with 0.05 to 9 is preferable, with 0.09 to 6 for better, 0.1 to 2 being the best, and be 20 to 100mPas to be good at 150 ℃ melt viscosity, with 25 to 98mPas is preferable, with 30 to 95mPas for better.

In low softening point phenol novolac resin of the present invention, if m/n surpasses 20, then second-order transition temperature can reduce, and it is generally acknowledged to have the tendency that flame retardant resistance is descended, so for not good.On the other hand, if m/n less than 0.04, then melt viscosity can improve and make mobile variation, so for not good.

Phenols used in the present invention, such as general formula (1) record, be on phenyl ring, to have a hydroxyl, R at least ¹, R ²Or R ³Also can substituted phenols.At this, R ¹, R ²And R ³Can be identical also can be different, a plurality of R ¹, R ²And R ³Separately can be identical also can be different, be the alkyl of hydroxyl or carbonatoms 1 to 6 respectively, respectively do for oneself 0 to 2 the substituting group group that integer constituted of p, q and r.With alkyl, for example can enumerate the alkyl of the carbonatoms 1 to 6 of straight or brancheds such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, these also comprise various isomer.

These phenols can use separately or mix more than 2 kinds and use.

Particularly, phenols for example can be enumerated phenol, cresols, ethylphenol, propylphenol, butylphenol, hexylphenol, xylenol, butyl methyl phenol etc. by the 1 valency phenol that alkyl replaced of 0 to 2 carbonatoms 1 to 6, also can enumerate catechol, Resorcinol, Resorcinol etc. in addition by 2 divalent phenol that hydroxyl replaced, be preferable with phenol wherein.

As the compound of the methylene-crosslinked base of formation of the present invention, suitable have formaldehyde.With regard to the form of formaldehyde, there is no particular restriction, but can use formalin and Paraformaldehyde 96, three

Alkane etc. decompose the polymkeric substance that forms formaldehyde in the presence of acid.

With the formalin of obtaining use easily is preferable, also can directly use 42% formalin of commercial goods.

The crosslinking group R that contains aryl used in the present invention can enumerate the divalence arylidene shown in above-mentioned general formula (2) and (3).

These divalence arylidene for example can enumerate 4,4 '-biphenylene, 3,3 '-biphenylene, 2,2 '-biphenylene, 2,4 '-biphenylene, 1,4-xylylene, 1,3-xylylene, 1,2-xylylene etc.The present invention is especially with 4 in these, and 4 '-biphenylene, 1,4-xylylene are preferable.

Contain the compound of the crosslinking group of aryl for importing above-mentioned substituent, concrete formation, can enumerate the compound shown in above-mentioned general formula (4) and (5).

In above-mentioned general formula (4) and (5), X is the alkoxyl group of halogen atom, hydroxyl or carbonatoms 1 to 6, R ⁴Alkyl for hydroxyl or carbonatoms 1 to 6.At this, halogen atom for example can be enumerated fluorine atom, chlorine atom, bromine atoms and iodine atom, is preferable with the chlorine atom wherein.Alkoxyl group for example can be enumerated the alkoxyl group of the carbonatoms 1 to 6 of straight or brancheds such as methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy, and these also comprise various isomer.Alkyl can be enumerated as above-mentioned substance.

For example can enumerate two (alkoxy methyl) biphenol compound of 4,4 '-two (methoxymethyl) biphenyl, 2,2 '-two (methoxymethyl) biphenyl, 2,4 '-two (methoxymethyl) biphenyl etc. for importing above-mentioned substituent concrete compound; Two (halogenation methyl) biphenol compound of 4,4 '-two (chloromethyl) biphenyl, 2,2 '-two (chloromethyl) biphenyl, 2,4 '-two (chloromethyl) biphenyl etc.; Two (methylol) biphenol compound of 4,4 '-two (methylol) biphenyl, 2,2 '-two (methylol) biphenyl, 2,4 '-two (methylol) biphenyl etc.; 1,4-two (methoxymethyl) benzene, 1,3-two (methoxymethyl) benzene, 1, two (alkoxy methyl) benzene compound of 2-two (methoxymethyl) benzene etc.; 1,4-two (chloromethyl) benzene, 1,3-two (chloromethyl) benzene, 1, two (halogenation methyl) benzene compound, 1 of 2-two (chloromethyl) benzene etc., 4-two (methylol) benzene, 1,3-two (methylol) benzene, 1, two (methylol) benzene compound of 2-two (methylol) benzene etc.; The hydroxy benzaldehyde compound of phenyl aldehyde, 2-hydroxy benzaldehyde, 3-hydroxy benzaldehyde, 4-hydroxy benzaldehyde etc.; The alkyl benzaldehyde compound of 2-tolyl aldehyde, 3-tolyl aldehyde, 4-tolyl aldehyde etc. etc.

For these isomer,, be preferable to use mixture of isomers though can use separately or mix use.

Again with the isomer mixture of Biphenylene compounds and/or xylylene compound for better.

The isomer of Biphenylene compounds and/or xylylene compound mixes, and with 1,4-body and 4,4 '-body contain the above situation of 50 moles of % at least for best.

But when mix using, this mixture ratio is with respect to 4,1 mole of 4 '-biphenylene, and 1, it is preferable that the 4-xylylene uses 20 to 50 moles of %.

[manufacture method of low softening point phenol novolac resin]

Manufacture method with the low softening point phenol novolac resin shown in the general formula (1), can be by in the presence of acid catalyst, with respect to a certain amount of phenols, add simultaneously n doubly the R of mole promptly contain compound and the m formaldehyde doubly mole of the crosslinking group of aryl in order to formation, carry out the method for 1 section condensation reaction and carry out.

At this moment, with respect to 1 mole of the total of the compound of the crosslinking group that contains aryl in order to formation and formaldehyde, phenols preferably uses 2 to 10 times of moles, 3 to 6 times of moles more preferably, more preferably more than 4 moles, simultaneously preferably in the following ways: under the temperature of reaction of low temperature (for example about 100 ℃), preferentially carry out the reaction of phenols and formaldehyde, the low-molecular-weight phenolic novolac that contains methylene-crosslinked base of main formation, then heat up or the increase catalytic amount, and make the phenolic novolac that contains methylene-crosslinked base, the compound that contains the crosslinking group of aryl in order to formation, and the phenols mode of reacting.

Employed acid catalyst is not particularly limited, can use separately or can and with organic acids such as mineral acid such as the example hydrochloric acid more than 2 kinds, oxalic acid, sulfuric acid, phosphoric acid and tosic acid etc., but serve as that the spy is good with sulfuric acid, oxalic acid or tosic acid.

The temperature of condensation reaction is 50 to 120 ℃ with cold condition, is preferable with 80 to 110 ℃ again; Temperature of reaction during intensification is 130 to 230 ℃, is preferable with 150 to 200 ℃.

The time of condensation reaction is according to the catalyst type of temperature of reaction or use and amount and change to some extent is about 1 to 24 hour.

About reaction pressure,, also can implement down in a small amount of pressurization or decompression though under normal pressure, carry out usually.

With respect to 1 mole of the total of the compound of the crosslinking group that contains aryl in order to formation and formaldehyde, the usage quantity of phenols is less than 2 moles of grades significantly under the situation away from above-mentioned reaction conditions, then may only obtain the phenolic novolac of high molecular and high melt viscosity, thus not good.

For this reason, low softening point phenol novolac resin of the present invention can be by making phenols and formaldehyde condensation in advance in the presence of acid catalyst, add then R in order to formation contain aryl crosslinking group compound and carry out condensation, the condensation reaction in 2 stages is made.The condensation reaction in these 2 stages can be added new phenols in the reaction in the 2nd stage.Be preferable with excessive use phenols equally this moment when also reacting with 1 section.For example in the reaction in the 1st stage with respect to 1 mole in formaldehyde, phenols with more than 2.5 moles, be preferably with 3.3 to 10 moles and exist; That is appended in the reaction in the 2nd stage contains the compound and the phenols of the crosslinking group of aryl in order to formation, with respect to the 1st to 2 stage add altogether contain 1 mole of the total of the compound of crosslinking group of aryl and formaldehyde in order to formation, the phenols that the 1st to 2 stage added altogether with more than 3 moles, to be preferably in 3.3 to 10 moles the scope be important.

If carry out such 2 stages condensation reaction, then contain aryl crosslinked fundamental mode phenolic novolac and contain the polymerization degree of each polymerized unit of the phenolic novolac of methylene-crosslinked base, that is the distribution of n and m can narrow down, become and be easy to control molecular weight, be easy to obtain the polymkeric substance of desired melt viscosity, therefore from realizing that purpose of the present invention is preferred.

One example of the condensation reaction in 2 stages is represented with following reaction formula.

The condensation reaction in 2 stages can be implemented according to the condition of 1 stage condensation reaction.

In above-mentioned 1 stage condensation reaction and the condensation reaction of 2 stages, it is different though the usage quantity of acid catalyst is complied with its kind, for the phenols that uses, if with oxalic acid then with about 0.1 to 2.0 quality %, if with sulfuric acid then with about 0.05 to 0.5 quality %, if with tosic acid then being good about 0.02 to 0.1 quality %.Especially when carrying out the condensation reaction in 2 stages, make in the crosslinking group that contains aryl and phenols and methylene-crosslinked baseline type novolac resin reacted in the 2nd stage, be preferable to use sulfuric acid or tosic acid.Again, there is no particular restriction for temperature of reaction, but be preferable with the scope that is set in about 60 to 160 ℃.Again with 80 to 140 ℃ for better.

After making its condensation reaction in the presence of the acid catalyst, remove unreacted phenols and acid catalyst, can obtain low softening point phenol novolac resin of the present invention.

Remove the method for phenols, generally can enumerate under reduced pressure or blow into rare gas element and heating simultaneously, the phenols distillation is got rid of the method to reactive system.The removal of acid catalyst can be enumerated by water etc. and the method for being cleaned.

In the manufacture method of low softening point phenol novolac resin of the present invention, in the usage quantity of the phenols of control raw material, the compound of crosslinking group that contains aryl in order to formation and formaldehyde, be set at as above-mentioned reaction conditions, thereby can obtain to have the resin of 150 ℃ of desired melt viscosities.

Low softening point phenol novolac resin of the present invention has following structure, that is: have the polymerized unit of the phenolic novolac of the phenolic novolac of aryl cross-linking type and methylene-crosslinked type with specific ratios simultaneously at intramolecularly, be applicable to the used for epoxy resin raw material that has both low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance and flame retardant resistance.

Moreover, low softening point phenol novolac resin of the present invention, can be widely used in purposes such as tackiness agent, coating agent, stacking material, shaped material, especially with regard to have low melting viscosity and high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance, and the characteristics of flame retardant resistance with regard to, be specially adapted to the hardener for epoxy resin that semiconductor-sealing-purpose, printed base plate insulation are used etc.

[epoxy resin cured product]

Low softening point phenol novolac resin of the present invention for example can be used as hardener for epoxy resin and uses.Epoxy resin cured product is by the phenol based polymer is mixed with Resins, epoxy and curing catalyst, makes its curing in 100 to 250 ℃ the temperature range and obtains.

With Resins, epoxy, for example can enumerate the Racemic glycidol ether type epoxy of bisphenol A type epoxy resin, bisphenol f type epoxy resin, cresol-novolak varnish (Cresol novolac) type Resins, epoxy, novolac-type Resins, epoxy, triphenol methane type Resins, epoxy, biphenyl type epoxy resin etc., glycidic ester type Resins, epoxy, glycidyl amine type epoxy resin, the Resins, epoxy that has the epoxy group(ing) more than two in the halogenated epoxy resin equimolecular.These Resins, epoxy can use separately, also can be also with more than 2 kinds.

(curing catalyst)

With curing catalyst, can use that to be used to make used for epoxy resin phenol be solidifying agent solidified, known curing catalyst.These curing catalysts can be enumerated organic phosphoric compound and boron salt, tertiary amine, quaternary ammonium salt, imidazoles and tetraphenyl boron salt thereof etc., but therein with regard to the viewpoint of solidified nature or wet fastness, with triphenyl phosphine and 1,8-two a word used for translation dicyclo (5.4.0) hendecene-7 (DBU, 1,8-diazabicyclo[5.4.0]-.undec-7-ene) be preferable.Moreover, higher for making flowability, preferably can represent the curing catalyst of active hot potentiality by heating, be good with the four benzene Phosphonium derivatives of four benzene Phosphonium tetraphenyl borates etc.

(other additive)

In the composition epoxy resin of the present invention, can add as required or react in advance and use inorganic filler, releasing agent, tinting material, fire retardant, low-stress agent etc.Especially be used in the semiconductor packages time spent, must add inorganic filler.These inorganic fillers can be enumerated amorphous silica, crystalline silica, aluminum oxide, glass, Calucium Silicate powder, gypsum, lime carbonate, wagnerite, clay, talcum, mica, magnesium oxide, barium sulfate etc., are preferable with amorphous silica, crystalline silica etc. especially wherein.The usage quantity of these additives is with identical the getting final product of usage quantity in the past the epoxy resin composition for semiconductor encapsulation.

Alkyl type resin of the present invention has an amount of phenolic novolac unit, when using as epoxy curing agent, can keep high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance, reach flame retardant resistance, and can realize lowering viscousity.

(embodiment)

List following embodiment, specify the present invention.And the appraisal procedure of the phenolic novolac of expression gained of the present invention.

(1) mensuration of ICI viscosity

ICI Cone ﹠amp; Plate viscometer: use TOA industry (thigh) MODEL CV-1S.

Flat board (Plate) temperature of setting the ICI viscometer is 150 ℃, the about 0.04g of weighing sample.

The resin of weighing is placed flat part, press down with taperer (Cone), placed 90 seconds by top.

Make the taperer rotation, read its torque value as ICI viscosity.

(2) mensuration of gel time

Resins, epoxy and phenol resins are added in the test tube with 1: 1 equivalent, again with TPP (Triphenylphosphine, triphenyl phosphine) being that the mode of 0.1wt% is measured and added in the test tube with respect to epoxy group(ing).

Test tube is arranged on to set oily temperature be on 150 ℃ the gel timer (the timer SFO-304M of Toshiba), uses the SUS stirring rod, stir with rotation in 1 second 1 time.

Though just begun to low viscous aqueous, through behind the certain hour, the viscosity of resin can rise rapidly, becomes gel.The spent therebetween time is gel time.

This time is short more, is the good index of solidified nature.

Will be when using as solidifying agent with the condition synthetic phenolic novolac (embodiment and comparative example) shown in the table 1, corresponding Resins, epoxy is the epoxidation biphenyl novolac resin of Japanese chemical drug (thigh) system NC-3000 (60 ℃ of softening temperatures, epoxy equivalent (weight) 270g/eq), and use triphenyl phosphine (Triphenylphosphine, also can note by abridging be TPP) as curing catalyst.

Low softening point phenol novolac resin of the present invention and above-mentioned Resins, epoxy are cooperated, and the ratio that makes phenolic hydroxyl group equivalent and epoxy equivalent (weight) is 1: 1, with respect to the weight epoxy of this cooperation with 1wt% adding TPP catalyzer.These are heated to 150 ℃ and melting mixing is watered behind the vacuum froth breaking (thickness 4mm) in the mould that casts from 150 ℃, 150 ℃ keep it is solidified after, solidified 5 hours and manufacture experimently out molding in 180 ℃ again.

The test method of the various rerum naturas of the molding of gained (cured article) is as follows.

(3) Tg (second-order transition temperature): TMA method (Thermal Mechanical Analysis, thermomechanical analysis) (5 ℃/minute of heat-up rates)

(4) water-intake rate: 24 hours boiling methods

(5) carbon yield

The proportional relation of carbon residue and oxygen index, the general high resin of flame retardant resistance is also referred to as carbon yield height (with reference to non-patent literature 1).Therefore, as the index of flame retardant resistance and measure.

(measuring method)

To downcut the square of length of side 1.5cm, gravimetry by above-mentioned cooperation solidified molding.

The sample that downcuts is put into crucible, burnt till 60 minutes with 800 ℃ electric furnace reductions.

After the cooling, the weight of working sample.

Heating made its ashing in 2 hours in 800 ℃ electric furnace again, measured its weight.

Try to achieve carbon yield (%) according to following formula.

Weight * 100 of carbon yield (%)=(weight after the weight-ashing after burning till)/sample

Embodiment 1

In having the glass reactor of whipping appts, prolong and nitrogen ingress pipe, add phenol 376g (4 moles), 4, (brief note is 4 to 4 '-dimethoxy methyl diphenyl, 4 '-BMMB) 226g (0.95 mole), 42% formalin 3.6g (0.05 mole), 50% aqueous sulfuric acid, 0.22 g were in 100 ℃ of reactions 1 hour.

Then, temperature of reaction is remained in 165 ℃ and make its reaction 3.5 hours.The methyl alcohol that is produced is removed in distillation therebetween.After reaction finishes,, carry out 3 washings with the reaction soln cooling of gained.Separate oil reservoir, remove unreacted phenol, obtain phenolic novolac (150 ℃ of melt viscosities: 90mPas) of 340g by underpressure distillation.

Use the phenolic novolac of gained, the rerum natura of the molding that will make with aforesaid method is shown in table 1.

Embodiment 2～12 and comparative example 1～5

Except the monomer that uses table 1 was formed, the method for putting down in writing with embodiment 1 made phenolic novolac.Again, the rerum natura with separately cured article is shown in table 1 in the lump.

Table 1

Monomer component (mole)	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
																		Phenol	4	4	4	3	4	4	8	4.3	4.3	4.3	4.3	4.3	4	3	4	2	1
4，4’-BMMB	0.95	?	0.8	0.8	0.5	0.7	0.75	0.7	0.6	0.5	0.4	0.15	1	1	0	0	0
																		4，4’-BCMB	?	0.9	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?
1，4-PXDM	?	?	?	?	0.4	?	?	?	?	?	?	?	?	?	?	?	?
																		42% formaldehyde	0.05	0.1	0.2	0.2	0.1	0.3	0.3	0.3	0.4	0.5	0.6	0.85	0	0	1	1	0.6
The m/n ratio	0.053	0.11	0.25	0.25	0.11	0.42	0.33	0.42	0.67	1.0	1.5	5.7	0	0	∞	∞	?
																		?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?
The resol characteristic	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?
																		ICI viscosity (150 ℃) [mPas]	90	80	60	95	70	55	40	52	45	40	33	26	105	185	20	50	200
?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?
																		The cured article characteristic	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?	?
Gelation time (minute)	-	-	-	-	-	-	-	14.2	14.8	14.4	13.7	13.2	-	-	-	-	-
																		Tg	144	135	130	140	133	105	90	125	124	121	123	120	139	154	-	135	142
Water-intake rate	0.65	0.66	0.68	0.66	0.67	0.98	1.10	1	0.72	0.73	0.73	0.83	0.65	0.62	-	0.83	0.70
																		Carbon yield	-	-	-	-	-	-	-	34.0	33.8	30.9	31.0	31.3	35.3	-	-	29.2	29.6

4,4 '-BMMB:4,4 '-two (methoxymethyl) biphenyl

4,4 '-BCMB:4,4 '-two (chloromethyl) biphenyl

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

(1) mensuration of ICI viscosity

ICI Cone ﹠amp; Plate viscometer: use TOA industry (thigh) MODEL CV-1S.

Make the taperer rotation, read its torque value as ICI viscosity.

Will be when using as solidifying agent with the condition synthetic phenolic novolac (embodiment and comparative example) shown in the table 2, corresponding Resins, epoxy is the epoxidation biphenyl novolac resin of Japanese chemical drug (thigh) system NC-3000 (60 ℃ of softening temperatures, epoxy equivalent (weight) 270g/eq), and uses triphenyl phosphine (also can note by abridging and be TPP) as curing catalyst.

Low softening point resol of the present invention and above-mentioned epoxy-Novolak resin are cooperated, and the ratio that makes phenolic hydroxyl group equivalent and epoxy equivalent (weight) is 1: 1, with respect to the weight epoxy of this cooperation with 1wt% adding TPP catalyzer.These are heated to 150 ℃ and melting mixing is watered behind the vacuum froth breaking (thickness 4mm) in the mould that casts from 150 ℃, 150 ℃ keep it is solidified after, made it to solidify 5 hours in 180 ℃ again, manufacture experimently out molding.

(2) Tg (second-order transition temperature): TMA method (Thermal Mechanical Analysis, thermomechanical analysis) (5 ℃/minute of heat-up rates)

(3) water-intake rate: 24 hours boiling methods

Embodiment 13

In having the glass reactor of whipping appts, prolong and nitrogen ingress pipe, add phenol 376g (4 moles), 4, (following brief note is 4 to 4 '-two (methoxymethyl) biphenyl, 4 '-BMMB) 143g (0.60 mole), 2, (brief note is 2 to 4 '-two (methoxymethyl) biphenyl, 4 '-BMMB) 36g (0.15 mole), 2, (brief note is 2 to 2 '-two (methoxymethyl) biphenyl, 2 '-BMMB) 48g (0.20 mole), 42% formalin 3.6g (0.05 mole), 50% aqueous sulfuric acid 0.22g were in 100 ℃ of reactions 1 hour.

Then, temperature of reaction is remained in 165 ℃ and make its reaction 3.5 hours.The methyl alcohol that is produced is removed in distillation therebetween.After reaction finishes,, carry out 3 washings with the reaction soln cooling of gained.Separate oil reservoir, remove unreacted phenol, obtain phenolic novolac (150 ℃ of melt viscosities: 29mPas) of 335g by underpressure distillation.

Embodiment 14～18 and comparative example 6～9

Except the component ratio with table 2 uses each monomer, with the synthetic phenolic novolac of the method for embodiment 13 records.The epoxy resin cured product of reentrying.Each rerum natura is shown in table 2 in the lump.

Table 2

Monomer component (mole)

Embodiment 13

Embodiment 14

Embodiment 15

Embodiment 16

Embodiment 17

Embodiment 18

Comparative example 6

Comparative example 7

Comparative example 8

Comparative example 9

Phenol

4

3

4

3

13

4，4’-BMMB

0.6

0.3

?

0.95

1

?

2，4’-BMMB

0.15

0.1

?

2，2’-BMMB

0.2

0.1

?

4，4’-BCMB

?

0.6

?

2，4’-BCMB

?

0.1

?

2，2’-BCMB

?

0.1

?

1，4-PXDM

?

0.4

?

0.65

?

1

?

1，2-PXDM

?

0.2

?

1，3-PXDM

?

0.05

?

1，4-PXDC

?

0.60

?

1，2-PXDC

?

0.15

?

1，3-PXDC

?

0.10

?

2-HBA

?

0.9

0.8

3-HBA

?

0.2

42% formaldehyde

0.05

0.1

0.2

0.05

0.15

0.05

0

0.1

0.45

The M/n ratio

0.053

0.11

0.25

0.055

0.176

0.053

0

0.11

0.45

?

The resol characteristic

?

ICI viscosity (150 ℃) [mPas]

29

50

30

35

30

95

105

100

600

88

?

The cured article characteristic

?

Tg

125

130

135

125

126

134

135

132

145

130

Water-intake rate

0.67

0.69

0.70

0.95

0.98

0.65

0.62

0.90

1.45

1.05

4,4 '-BMMB:4,4 '-two (methoxymethyl) biphenyl

2,4 '-BMMB:2,4 '-two (methoxymethyl) biphenyl

2,2 '-BMMB:2,2 '-two (methoxymethyl) biphenyl

4,4 '-BCMB:4,4 '-two (chloromethyl) biphenyl

2,4 '-BCMB:2,4 '-two (chloromethyl) biphenyl

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

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

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

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

1,4-PXDC:1,4-two (chloromethyl) benzene

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

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

The 2-HBA:2-hydroxy benzaldehyde

The 3-HBA:3-hydroxy benzaldehyde

As shown in table 2, the phenolic novolac of gained and contain the cured article of this resin among the embodiment 13～18 have both low melting viscosity, high glass transition temperature and agent of low hygroscopicity with good balance, but any one physics value reduces all in comparative example 6～9.

According to the present invention, can provide have low melting viscosity, high glass transition temperature, agent of low hygroscopicity, high adherence, thermotolerance and excellent in flame retardance, especially be suitable as the novel phenolic novolac of the Resins, epoxy use that electric industry and electronic industry are used, packaging of electronic parts is used, the plywood material is used, and with this phenolic novolac epoxidation novolak condenses of obtaining of epoxidation in addition, and with its with the hardener for epoxy resin reaction epoxy resin cured product of acquisition.In addition, the phenolic novolac that contains biphenylene can be used as fire retardant and uses.

Claims

1. a low softening point novolac resin, characterized in that:

Contain the structural unit represented by following general formula (1),

In the formula, R represents at least one divalent group selected from groups represented by the following general formula (2),

It can also contain structural units represented by the following general formula (3),

In the formula, R ⁴ is a hydroxyl group or an alkyl group with 1 to 6 carbon atoms,

m and n are numbers satisfying m/n ranging from 0.04 to 20, R ¹ , R ² and R ³ may be the same or different, and are respectively hydroxyl or an alkyl group with 1 to 6 carbon atoms, and p, q and r are respectively is an integer from 0 to 2; and, the melt viscosity of the novolak resin at 150° C. is 20 to 100 mPa·s.

2. low softening point novolac resin according to claim 1, wherein, R contains the group represented by following formula at least,

3. low softening point novolac resin according to claim 1, wherein, following formula

The groups indicated are mixtures of individual isomers.

4 . The low softening point novolac resin according to claim 1 , wherein m/n is a numerical value satisfying 0.05 to 9. 4 .

5. The low softening point novolac resin according to claim 1, wherein the melt viscosity is 25 to 90 mPa·s.

6. The manufacture method of the low-softening point novolak resin described in any one of claims 1 to 5, characterized in that, phenols, selected from substituent subunits as shown in the following general formula (4) At least one of a phenyl compound and a substituted benzene compound, and formaldehyde are condensed in the presence of an acid catalyst,

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

7. the manufacture method of low softening point novolak resin according to claim 6, wherein, also contain the benzaldehyde compound shown in following general formula (5) except the compound of above-mentioned formula (4),

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

8. the manufacture method of low softening point novolac resin according to claim 6 or 7, comprises the following steps:

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

(2) Condensation of phenols by 3 mole times or more.

9. The method for producing a low softening point novolak resin according to claim 8, wherein the acid catalyst is at least one compound selected from the group consisting of sulfuric acid, hydrochloric acid, oxalic acid, and p-toluenesulfonic acid.

10. A cured product, which contains a low softening point novolak resin selected from any one of claims 1 to 5, and a product made by the production method according to any one of claims 6 to 9. At least one resin component in the obtained low softening point novolak resin.

11. A cured epoxy resin obtained by reacting the cured product according to claim 10 with an epoxy resin.