JPH0625393A - Phenol polymer, its production and use thereof - Google Patents

Abstract

PURPOSE:To obtain a new phenol polymer excellent in resistance to heat and moisture, etc., useful as, e.g. a curing agent for epoxy resins by condensation between a dihydroxy compound and xylylene compound each having specific structure in the presence of an acid catalyst. CONSTITUTION:This phanol polymer 300-10000 in average molecular weight and 50-160 deg.C in softening point can be obtained by condensation, in the presence of an acid catalyst (e.g. sulfuric acid), between (A) a dihydroxy compound of formula HOA-OH [A is of formula I or formula II (R1 and R2 are each H, 1-9C alkyl, etc.; X is S, O, etc.)] (e.g. 2,2'-dihydroxybiphenyl)and (B) a xylylene compound of formula III (R is halogen, hydroxyl group, etc.) (pref, alpha,alpha'- dichloro-p-xylene) at the molar ratio A/B of (5:1) to (1:1) pref. 130-180 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenolic polymer, a method for producing the same and its use. This phenolic polymer can be used as a raw material for epoxy resin, a curing agent for epoxy resin, or a molding material obtained by curing hexamethylenetetramine (hexamine). For example, it is suitable as an epoxy resin composition for applications such as casting, lamination, adhesion, molding, encapsulation, and composite materials. More specifically, it is useful as an IC encapsulation material and is cured by hexamine. As a molding material, it can be used in applications such as electricity, automobiles, machinery, building materials, and other composite materials.

[0002]

2. Description of the Related Art The use of phenolic resins as matrix resins for heat-resistant composite materials and heat-resistant molding materials has become more and more diversified in recent years and has become industrially important. In these advanced fields, the phenolic resin itself is required to have high performance, such as heat resistance and
Performance improvements such as mechanical properties, oxidation stability, and moisture resistance are required. Conventionally, as a typical structure of a phenol resin, a novolac resin produced by phenols and formalin is known. Since this novolak resin is inexpensive, it is industrially used in many fields.
However, this novolac resin has a drawback that it is inferior in moisture resistance and oxidation stability in addition to the drawback that it is essentially brittle, and its use in the above-mentioned advanced fields is limited.

In recent years, for the purpose of improving novolac resins, a phenol aralkyl resin composed of a phenol and a p-xylylene compound (Japanese Patent Publication No. 47-15111) and a phenol dicyclopentadiene resin composed of a phenol and a dicyclopentadiene (Japanese Patent Laid-open Publication No. 63-99224) has been developed and is partially used. However, in the former case, although the moisture resistance and the oxidation resistance are excellent, the epoxy cured product and the hexamine cured product are considered to have a problem of insufficient curing during heating. Further, the heat distortion temperature, which is a measure of heat resistance, is low, and improvement thereof is desired. On the other hand, in the latter case,
In the same field, it has been recognized that it has excellent moisture resistance and heat resistance, but on the other hand, it has the drawbacks that it is hard and brittle and that the curing reaction is slow due to the steric hindrance of the linking group.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks, to develop a useful phenol polymer, and to use it for the purpose. That is, it is intended to provide a phenol resin excellent in heat resistance, moisture resistance, oxidation stability, mechanical characteristics, reactivity in curing, etc., an epoxy resin composition using the same, and a hexamine-containing composition.

[0005]

The inventors of the present invention have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention has the general formula (I)
A dihydroxy compound represented by: HO-A-OH (I) (In the formula, A represents the following group (Chemical Formula 3),

[0006]

[Chemical 3] R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an aryl group, X is a direct bond, —S—, —O—, an alkylene group having 1 to 9 carbon atoms, An arylene group or a cycloalkylene group) and a xylylene compound represented by the general formula (II)

[0007]

[Chemical 4] (In the formula, R is a halogen atom, a hydroxyl group or a carbon number of 1 to 4
Represents a lower alkoxy group of

And a compound (I) / (II) molar ratio of 5
The average molecular weight of 300 to 10000 and the softening point range of 50 to 160 are used in the condensation reaction in the presence of an acid catalyst.
The invention relates to a method for producing a phenol polymer at 0 ° C and a phenol polymer obtained by this production method, and further, in a resin composition containing a polyfunctional epoxy compound and a curing agent, the curing agent contains the above-mentioned phenol polymer. An epoxy resin composition, a polyfunctional epoxy compound, a curing agent, a resin composition containing an inorganic filler, wherein the curing agent contains an epoxy resin composition containing the phenol polymer, a phenol polymer, hexamethylene tetramine In the composition, the phenol polymer relates to a molding material composition containing the above-mentioned phenol polymer.

The phenolic polymer of the present invention comprises dihydroxy compounds having a relatively high functional group density, which are further linked by a xylylene group. Therefore, in applications using this phenol polymer, excellent properties can be realized without impairing various properties such as heat resistance, moisture resistance, oxidation stability, and curing reactivity. In particular, it is recognized that the curing reactivity is improved by using a phenol polymer having a thioether bond as a curing agent for epoxy resin.

The method for producing this phenol polymer will be described below. The dihydroxy compound used in the present invention is represented by the above general formula (I), and specifically,
2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl,
2,2'-thiodiphenol, 2,4'-thiodiphenol, 4,4'-thiodiphenol, 2,2'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,
4'-thiocresol, 4,4'-dihydroxydiphenyl ether, 2,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 3,3 '
-Dimethyl-4,4'-dihydroxydiphenylmethane, 1,1-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane,
1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 2,2-bis (4'-hydroxyphenyl)
Propane, 2- (4'-hydroxyphenyl) -2-
(3′-hydroxyphenyl) propane, 2,2-bis (3′-methyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-isopropyl-4′-hydroxyphenyl) propane, 2,2 -Bis (3'-cyclohexyl-4'-hydroxyphenyl) propane, 1,
1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 2,2
-Bis (4'-hydroxyphenyl) adamantane,
1,2-bis (4'-hydroxyphenyl) ethane,
2,2-bis (4'-hydroxyphenyl) butane, 1,
1-bis (4'-hydroxyphenyl) isobutane,
2,2-bis (4'-hydroxyphenyl) octane,
1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,
Examples thereof include 7-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene, but are not limited thereto. Moreover, these can also be used in combination of 2 or more types.

The xylylene compound used in the present invention is represented by the general formula (II), in which R is preferably chlorine, bromine, iodine, fluorine, a hydroxyl group or a lower alkoxy group having 4 or less carbon atoms, With 4 or more alkoxy groups, the reaction is slow. In addition, when the number of carbon atoms is 4, that is, in the butoxy group, the reaction tends to be slow in the tert-butoxy group.
Therefore, suitable for use in the present invention are:
α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dibromo-p-xylene, α, α′-diiodo -P-xylene, α, α'-dihydroxy-p-
Xylene, α, α′-dihydroxy-m-xylene,
α, α′-dimethoxy-p-xylene, α, α′-dimethoxy-m-xylene, α, α′-dimethoxy-o-xylene, α, α′-diethoxy-p-xylene, α,
α'-di-n-propoxy-p-xylene, α, α'-
Diisoropoxy-p-xylene, α, α′-di-n-butoxy-p-xylene, α, α′-di-sec-butoxy-p-xylene, α, α′-diisobutoxy-p-xylene and the like can be mentioned. .

In the reaction of the present invention, 1 mol of the xylylene compound represented by the general formula (II) is added in an amount of 1 to 5 mol, preferably 1.1 to 3 mol, and the mixture is heated in the presence of an acid catalyst. Do it. The reaction temperature is 11
The temperature is preferably 0 ° C or higher, and the reaction becomes extremely slow at 110 ° C or lower. Further, in order to make the reaction time as short as possible, the reaction temperature is preferably in the range of 130 to 250 ° C, and more preferably in the range of 130 to 180 ° C. The reaction time is about 1 to 30 hours. Examples of the acid catalyst include inorganic or organic acids, for example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, zinc chloride, aluminum chloride and stannic chloride. Friedel-Crafts type catalysts such as ferric chloride, sulfuric acid esters such as dimethylsulfate and diethylsulfate, and super strong acids such as trifluoromethanesulfonic acid and boron trifluoride can be used alone or in combination. . The amount of catalyst used is about 0.0 of the total weight of the raw materials charged.
001 to 10% by weight, preferably 0.001 to 1% by weight
It is a degree.

When R is halogen in the xylylene compound of the general formula (II), a method of reacting with an alkali metal salt of a dihydroxy compound to obtain a benzyl ether type and transferring this with an acid catalyst is also possible. When such a method is adopted, the reaction temperature can be set lower than that of the Friedel-Crafts reaction. That is, both the benzyl etherification reaction and the transfer reaction proceed at 40 ° C or higher, but preferably in the range of 50 to 150 ° C. The acid catalyst used in the Friedel-Crafts reaction is used as the acid catalyst in the transfer reaction. Further, in the reaction of reacting the alkali metal salt of the dihydroxy compound and the xylylene compound, it is usually preferable to react in a water-immiscible solvent such as benzene, toluene, chlorobenzene and the like in a two-layer system of water,
After the reaction, it is possible to shift to the next transfer reaction by a treatment such as liquid separation and washing with water.

In addition, the method other than the above for producing the phenolic polymer of the present invention is usually carried out without using a solvent, but a solvent inert to the reaction may be used. Examples of these solvents include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol and diethylene glycol, ethers such as methoxyethanol, ethoxyethanol, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and aromatic carbons such as toluene and xylene. Hydrogen, 1,
2-dichloroethane, 1,1,2-trichloroethane,
Examples thereof include halogenated hydrocarbons such as monochlorobenzene, aprotic polar solvents such as dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. The amount of these solvents used is appropriately selected from a small amount for suspending the reaction raw material system to an amount sufficient to uniformly dissolve the reaction raw material system, but it is usually 10 wt% to 300 wt% of the total raw material.

The reaction may be carried out by any method such as a method of charging the raw materials all at once and reacting, or a method of adding a xylylene compound to a mixture of a dihydroxy compound and a catalyst and sequentially reacting them. To be selected. Hydrogen halide, water, alcohol or the like produced as the reaction proceeds is trapped and removed outside the system. After completion of the reaction, the volatile components are removed, discharged as it is, and cooled to obtain a hard and brittle phenol polymer of the present invention. Further, the resin in which the unreacted dihydroxy compound has been removed by means such as vacuum distillation or extraction with an alkaline aqueous solution and washing with water before discharging is also the phenol polymer of the present invention. The phenol polymer of the present invention thus obtained has an average molecular weight of 300 to 10,000 and a softening point (JIS-K-2548).
It is in the range of 40 to 160 ° C. (using a ring and ball softening point measuring device). Further, in the case of a curing agent for an epoxy resin or the like, especially when reduction of unreacted dihydroxy compound is required, the content of the remaining unreacted dihydroxy compound is preferably 5 wt% or less.

Next, an epoxy resin composition using such a phenol polymer of the present invention as a curing agent will be described. The polyfunctional epoxy resin used in the resin composition of the present invention contains two or more epoxy groups in one molecule, and includes, for example, phenol novolac type epoxy resin and o-cresol novolac type epoxy resin. Epoxidized novolac resin of phenols and aldehydes, epoxide of aralkyl resin by xylylene bond such as phenol and naphthol, epoxidation of phenoldicyclopentadiene resin, bisphenol A, bisphenol F, bisphenol S, biphenol, substitution Diglycidyl ethers such as biphenol and dihydroxynaphthalene, polybasic acids such as phthalic acid and dimer acid, and glycidyl ester type epoxy resins obtained by reaction of epichlorohydrin, diaminodiphenylmethane, diamid Diphenyl sulfone, include glycidylamine type epoxy resins obtained by reaction of a polyamine with epichlorohydrin, such as isocyanuric acid, it may be used in combination even these at an appropriate number of types.

In the epoxy resin composition of the present invention,
The phenolic polymer is used as a curing agent for these epoxy resins. In this case, the curing agent may be used in combination with widely used compounds other than the phenol polymer of the present invention. These are, for example:
Phenol, cresol, xylenol, resorcin,
Novolak-type phenol resin obtained by condensation reaction of phenols such as catechol, bisphenol A and bisphenol F with formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under acidic catalyst, aralkyl resin with xylylene bond such as phenol and naphthol , Phenoldicyclopentadiene resin, etc., and these may be used alone or in combination of two or more kinds. The equivalent ratio with the epoxy resin is not particularly limited, but is 0.5-1.
5 is preferable.

The epoxy resin composition of the present invention further comprises
An inorganic filler can be blended and used. As the inorganic filler used, silica, alumina, silicon nitride, silicon carbide, talc, calcium silicate, calcium carbonate,
Examples thereof include powders such as mica, clay and titanium white, and fiber bodies such as glass fiber and carbon fiber. Of these, crystalline silica and / or fusible silica are preferable from the viewpoint of thermal expansion coefficient and thermal conductivity. Further, considering the fluidity of the resin composition at the time of molding, its shape is preferably spherical or a mixture of spherical and amorphous. The blending amount of the inorganic filler is 100 with respect to the total weight of the epoxy resin and the curing agent.
~ 900 wt% is necessary, preferably 2
It is from 00 to 600% by weight.

In the present invention, it is desirable to add various additives from the viewpoints of mechanical strength and heat resistance. That is, it is preferable to use a coupling agent in combination for the purpose of improving the adhesiveness between the resin and the inorganic filler. Examples of such coupling agents include silane-based, titanate-based, aluminate-based and zircoaluminate-based couplings. Agents can be used. Of these, silane coupling agents are preferable, and silane coupling agents having a functional group that reacts with an epoxy resin are most preferable. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-
Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
Examples thereof include 3-mercaptopropyltrimethoxysilane, and these can be used alone or in combination. These silane coupling agents are preferably immobilized in advance on the surface of the inorganic filler by adsorption or reaction.

In the present invention, it is desirable to use a curing accelerator when curing the resin composition.
As such a curing accelerator, 2-methylimidazole,
Imidazoles such as 2-methyl-4-ethylimidazole and 2-heptadecylimidazole, amines such as triethanolamine, triethylenediamine and N-methylmorpholine, organic phosphines such as tributylphosphine, triphenylphosphine and tritolylphosphine ,
Tetraphenylphosphonium tetraphenylborate,
There are tetraphenylborones such as triethylammonium tetraphenylborate, 1,8-diaza-bicyclo (5,4,0) undecene-7 and its derivatives. The above curing accelerators may be used alone or in combination of two or more kinds, and the mixing ratio of these curing accelerators is 0.01 to 100 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. Used in the range of 10 parts by weight.

In the resin composition of the present invention, in addition to the above-mentioned components, if necessary, a releasing agent such as fatty acid, fatty acid salt and wax, a flame retardant such as bromine compound, antimony and phosphorus,
Coloring agents such as carbon black, various silicone oils, etc. may be blended, mixed and kneaded to obtain a molding material.

Next, a molding material composition containing the phenol polymer of the present invention and hexamethylenetetramine will be described. These include the phenol polymer of the present invention as an essential component and, if necessary, may be used in combination with other phenol resins. Hexamethylenetetramine, and, if necessary, an inorganic filler or wood flour, for this phenol polymer. It can be obtained by adding a curing accelerator, a pigment, a lubricant, a rust preventive, a stabilizer and the like. Other phenolic resins used in combination with the phenolic polymer of the present invention include, for example, phenol,
Cresol, xylenol, resorcin, catechol,
Phenols such as bisphenol A and bisphenol F, and a novolac type phenol resin obtained by condensation reaction of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under an acidic catalyst, aralkyl resin by xylylene bond such as phenol and naphthol, There are phenol dicyclopentadiene resins and the like, and these may be used alone or in combination of two or more kinds.

Further, in the molding material composition of the present invention, an inorganic filler, wood powder or a curing accelerator may be used. As the inorganic filler, for example, asbestos, mica, glass fiber,
Carbon fibers, silica, alumina, calcium carbonate, magnesium oxide and the like, and examples of the curing accelerator include organic acids. These are, for example, benzoic acid, salicylic acid, cinnamic acid, p-toluenesulfonic acid and the like.
The ratio of the inorganic filler or wood powder to the resin component is usually 0.3 to 4: 1 by weight. The amount of organic acid used as a curing accelerator is 0.02 to hexamine.
A weight ratio of 0.5. The amount of hexamine used is
Usually, it is used in an amount of 8 to 20% by weight based on the resin component. The molding material composition of the present invention is based on the above components,
A molding material can be obtained by mixing and kneading at 120 ° C. by a roll mill.

[0024]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 4,4′-thiodiphenol 1090 g (5 mol) and α, α′-dimethoxy-p-xylene 415 g in a reactor.
(2.5 mol) was charged and dissolved by heating. Inner temperature 130
At 0 ° C., with stirring, 1.5 g of catalytic methanesulfonic acid was added. Slowly raise the temperature to 8 at an internal temperature of 155 ° C to 160 ° C.
Aged for hours. On the way, the produced methanol was distilled out of the system. After aging, the volatile matter was removed under reduced pressure of an aspirator and immediately discharged to a porcelain dish. Yield 1220
g. The obtained reddish brown phenolic polymer was composed of a thioether bond and a p-xylylene bond, and had a softening point (SP) of 79 ° C. and an average molecular weight (Mw) of 3,200. The hydroxyl equivalent (OH value) was 143 g / eq.

Synthesis Examples 2 to 7 In Synthesis Example 1, the kinds of the dihydroxy compound and the xylylene compound were changed as shown in Table 1 (Table 1), and Synthesis Example 1 was changed.
The same procedure was followed to obtain a phenol polymer. The results are shown in Table 1.

[0026]

[Table 1]

Synthesis Example 8 1140 g (5 mol) of bisphenol A was added to a reactor.
875 g (2.5 mol) of α, α'-dichloro-p-xylene and 2000 ml of toluene were charged, and the internal temperature was raised to 70 ° C while stirring. Then, 2500 g (6.25 mol) of a 10% aqueous caustic soda solution was added dropwise over 1 hour. Then, it was aged for 10 hours under reflux. Next, the reaction solution is cooled to 50 ° C. and then diluted with dilute hydrochloric acid.
It neutralized to H = 6 and left still. After separating into two layers, the lower layer portion was removed, and further water separation was performed to obtain a uniform transparent toluene solution. Next, 3 g of methanesulfonic acid was added to this toluene solution and aged at a temperature of 55 to 56 ° C. for 7 hours to complete the reaction. 25 g of a 10% aqueous barium hydroxide solution was added to this solution to neutralize it, and then heated to distill off toluene. Volatile components were completely removed under a vacuum of an aspirator and discharged as it was to obtain a reddish brown transparent phenol polymer. Yield 1320g, softening point 81
C., average molecular weight 1120, hydroxyl equivalent is 151 g / e
It was q.

Synthesis Example 9 160 g of 2,6-dihydroxynaphthalene was placed in a reactor.
(1 mol), α, α′-dichloro-p-xylene 70 g
(0.4 mol) and 50 ml of diethylene glycol dimethyl ether were charged, the temperature was raised with stirring, and the internal temperature was adjusted to 1
The reaction was terminated by maintaining the temperature at 50 ° C to 160 ° C and aging for 7 hours. Next, diethylene glycol dimethyl ether was distilled off under vacuum and discharged into hot water. After extraction with stirring, the water layer was removed by decanting. After this hot water extraction operation was repeated 3 times, the dark brown phenol polymer was heated to remove water, and immediately discharged into a porcelain dish. The yield was 188 g, the softening point was 127 ° C, and the average molecular weight was 570.
The unreacted raw material component was 2.3 wt%. The hydroxyl equivalent was 111 g / eq.

Examples 1 to 7 o-cresol novolac type epoxy resin (EOCN-102S; manufactured by Nippon Kayaku Co., Ltd.) was used as an epoxy resin for the phenolic polymers produced in Synthesis Examples 1, 4, 6, 7, and 8. ), Diglycidyl ether of 1,6-dihydroxynaphthalene (Epiclone EXA-4032; manufactured by Dainippon Ink and Chemicals), 4,4′-dihydroxy-3,3 ′,
A cured product obtained by blending diglycidyl ether of 5,5'-tetramethylbiphenyl (YX-4000H; manufactured by Yuka Shell Co., Ltd.) in a ratio shown in Table 2 (Table 2), and casting the mixture. Was measured. Test pieces for measuring physical properties are transfer molded (180 ° C, 30 kg / c
m ² , 3 min). The results are shown in Table 2.

Comparative Example 1 An o-cresol novolac type epoxy resin (EOCN-102S) was used as an epoxy resin, and a phenol novolac resin (BRG # 558) was used as a curing agent.
A cured product was obtained in the same manner as in Example 1. The results of measuring the physical properties of the obtained cured product are shown in Table 2.

[0031]

[Table 2]

Examples 8 to 14, Comparative Example 2 The epoxy resin compositions of Examples 1 to 7 and Comparative Example 1 were
Various fillers were added in the formulations shown in Table 3 (Table 3), and cast processing was performed in the same manner to obtain a cured product, and the physical properties of this were measured.
Further, using a mixture having the same composition, a test element (10 mm × 10 mm square) was mounted on the element mounting portion of the lead frame for a flat package type semiconductor device, and then transfer molding (180 ° C., 30 kg / cm ² , 3 mi
From n), a semiconductor device for test was obtained. Using this test semiconductor device, V.I. P. An S test (crack generation test) was performed. The results are shown in Table 3 (Table 3).

[0033]

[Table 3]

The symbols, substances and measuring methods used in Tables 2 and 3 are shown below. -EOCN-102S; o-cresol novolac type epoxy resin (manufactured by Nippon Kayaku) Epoxy equivalent 214 g / e
q-Epiclone EXA-4032; naphthalene type epoxy resin (Dainippon Ink and Chemicals, Inc.) epoxy equivalent 147g
/ Eq · YX-4000H; Biphenyl type epoxy resin (Oilized Ciel epoxy) epoxy equivalent 190g / eq · BRG # 558; Phenol novolac resin (Showa High Polymer) OH value 104g / eq · Phenol dicyclopentadiene resin; Mitsui Toatsu Chemical (DPR-5000) A phenol resin represented by the general formula (3) (Chemical formula 5), having an average molecular weight of 530 and an OH value of 173 g / eq.

[0035]

[Chemical 5] -Phenol Zyloc resin; manufactured by Mitsui Toatsu Chemicals (Mirex XL-225LL) A phenol resin represented by the general formula (4) (Chemical formula 6), having an average molecular weight of 1280 and an OH value of 174 g / eq.

[0036]

[Chemical 6] ・ Naphthol syloc resin; manufactured by Mitsui Toatsu Chemicals (α-N
X) A naphthol resin represented by the general formula (5) (chemical formula 7), having an average molecular weight of 640 and an OH value of 220 g / eq.

[0037]

[Chemical 7]

C11Z; undecyl imidazole (manufactured by Shikoku Fine Chemicals) inorganic filler; spherical fused silica (Harimic S-CO)
A mixture of 50 parts by weight of Micron Co., Ltd. and 50 parts by weight of amorphous fused silica (Hugh Rex RD-8, manufactured by Tatsumori Co., Ltd.)-Silane coupling agent; (SZ-6083, manufactured by Toray Dow Corning Silicone)・ Glass transition temperature; TMA method (Shimadzu, measured by TMA-system DT-30) ・ Bending strength, elastic modulus; JIS K-6911 ・ Boiling water absorption rate: measuring weight increase after boiling for 2 hours in boiling water at 100 ° C ・V. P. S test; test semiconductor device at 65 ° C
After leaving it in a 95% constant temperature and humidity chamber for 168 hours, immediately after that, a 215 ° C Freonate solution (Sumitomo 3M, FC
-70), and the number of semiconductors in which the package resin was cracked was counted. The test value is shown by a fraction, the numerator is the number of semiconductor devices in which a crack has occurred, and the denominator is the number of semiconductor devices used in the test.

Examples 15 to 16 and Comparative Examples 3 to 5 Phenol polymers obtained in Synthesis Examples 1, 4, and 8 and, as a comparison, phenol novolac resin # 2000.
(Showa High Polymer Co., Ltd.), Phenol Zyloc Resin (Mitsui Toatsu Chemical Co., Ltd .; Milex 225, average molecular weight 2400),
Using phenol dicyclopentadiene resin (manufactured by Mitsui Toatsu Chemicals; DPR-3000, average molecular weight 720), hexamethylenetetramine was added at a ratio shown in Table 4 (Table 4), and the mixture was roll-kneaded at 120 ° C. for 5 minutes to obtain a molding material. A composition for use was obtained. These compositions were compression molded at 190 ° C. for 5 minutes to obtain test pieces for evaluation of physical properties. In addition, post-curing was performed under the following conditions except for the hardness measurement, and the test was performed. The results are shown in Table 4.・ Post cure conditions 170 ° C / 16hr + 220 ° C / 4hr + 250 ° C / 4
hr

[0040]

[Table 4]

[0041]

As described above in detail, the resin composition using the phenolic polymer of the present invention is useful for encapsulating materials and molding materials. These give excellent performances such as moisture resistance, heat resistance and mechanical properties which have been conventionally demanded. Further, since such a phenol polymer can be produced by a simple method, it greatly contributes to industrial development.

Claims (5)

[Claims] 1. A dihydroxy compound HO-A-OH (I) represented by the general formula (I) (wherein A represents the following group (Formula 1), and R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or an aryl group, X is a direct bond, —S—, —O—, an alkylene group having 1 to 9 carbon atoms, An arylene group or a cycloalkylene group) and a xylylene compound represented by the general formula (II) (Chemical Formula 2) (In the formula, R is a halogen atom, a hydroxyl group or a carbon number of 1 to 4
Represents a lower alkoxy group of the formula (I) / (I
I) in a molar ratio of 5/1 to 1/1 in the presence of an acid catalyst, the condensation reaction is characterized by an average molecular weight of 300 to
A method for producing a phenolic polymer having a softening point range of 50 to 160 ° C in the range of 10,000. 2. A phenolic polymer obtained by the production method according to claim 1. 3. A resin composition containing a polyfunctional epoxy compound and a curing agent, wherein the curing agent contains the phenol polymer according to claim 2. 4. A resin composition containing a polyfunctional epoxy compound, a curing agent, and an inorganic filler, wherein the curing agent contains the phenol polymer according to claim 2. 5. A composition for a molding material, which comprises a phenolic polymer and hexamethylenetetramine, wherein the phenolic polymer contains the phenolic polymer according to claim 2.