JP3166936B2 - Phenolic polymer, its production method and its use - Google Patents

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. The phenol polymer can be used as a raw material for an epoxy resin, a curing agent for an 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, laminating, bonding, molding, sealing, and composite materials. More specifically, the epoxy resin composition is useful as an IC sealing material. As a molding material, it can be used in applications such as electricity, automobiles, machines, 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 been increasingly diversified in recent years and has become industrially important. In these advanced fields, high performance is required for the phenolic resin itself, for example, heat resistance,
Improvements in performance such as mechanical properties, oxidation resistance, and moisture resistance have been demanded. Conventionally, as a typical structure of a phenol resin, a novolak resin produced from phenols and formalin is known. Since the novolak resin is inexpensive, it is industrially used in many fields.
However, this novolak resin has a drawback that it is inferior in moisture resistance and oxidation resistance in addition to a drawback that it is inherently brittle, and its use in advanced fields as described above is limited.

In recent years, phenol aralkyl resins comprising phenols and p-xylylene compounds (JP-B-47-15111) and phenol dicyclopentadiene resins comprising phenols and dicyclopentadiene (JP-A No. 63-99224) has been developed and partially used. However, in the former case, although moisture resistance and oxidation resistance are excellent, shortage of thermal curing in epoxy cured products and hexamine cured products is regarded as a problem. Further, the heat distortion temperature, which is a measure of heat resistance, is also low, and its improvement is demanded. On the other hand, in the latter case,
In the same field, excellent characteristics of moisture resistance and heat resistance are recognized, but on the other hand, they have disadvantages of being hard and brittle, and having a low curing reactivity due to steric hindrance of the linking group.

[0004]

An object of the present invention is to solve the above-mentioned drawbacks, develop a useful phenolic polymer, and provide it for its use. That is, an object of the present invention is to provide a phenol resin excellent in heat resistance, moisture resistance, oxidation stability, mechanical properties, reactivity in curing, and the like, an epoxy resin composition using the same, and a hexamine-containing composition.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a compound represented by the general formula (I):
Dihydroxy compound represented by the following formula (3)

Embedded image

(Wherein R ₁ and R ₂ are hydrogen atoms, carbon atoms 1
And X represents an alkyl group, a cycloalkyl group or an aryl group, X represents —S—, —O—, an alkylene group or a cycloalkylene group having 5 to 10 carbon atoms) and a general formula (I
I) Xylylene compound represented by Chemical formula 4

[0007]

Embedded image (In the formula, R is a halogen atom, a hydroxyl group, or a group having 1 to 4 carbon atoms.
Represents a lower alkoxy group)

And a compound (I) / (II) molar ratio of 5
/ 1 to 1/1, average molecular weight of 300 to 10,000 for condensation reaction in the presence of an acid catalyst, softening point of 50 to 160
The present invention relates to a method for producing a phenolic polymer at ℃ and a phenolic polymer obtained by this producing method, further comprising a polyfunctional epoxy compound, a resin composition containing a curing agent, wherein the curing agent contains the phenolic polymer. Epoxy resin composition, a polyfunctional epoxy compound, a curing agent, in a resin composition containing an inorganic filler, the curing agent contains the phenolic polymer-containing epoxy resin composition, phenolic polymer, hexamethylenetetramine In the composition, the phenol polymer relates to a composition for a molding material containing the phenol polymer.

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

Hereinafter, a method for producing the phenol polymer will be described. The dihydroxy compound used in the present invention is represented by the above general formula (I).
2'-thiodiphenol, 2,4'-thiodiphenol, 4,4'-thiodiphenol, 2,2'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,
4′-thiocresol, 4,4′-dihydroxydiphenyl ether, 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)
And adamantane. These compounds may be used in combination of two or more.

The xylylene compound used in the present invention is represented by the general formula (II), wherein R is preferably chlorine, bromine, iodine, fluorine, a hydroxyl group or a lower alkoxy group having 4 or less carbon atoms. With four or more alkoxy groups, the reaction is slow. In addition, a reaction having a carbon number of 4, that is, a tert-butoxy group tends to be slow in a butoxy group.
Thus, those suitable for use in the present invention include:
α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dibromo-p-xylene, α, α′-diiodine -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'-
Diisolopoxy-p-xylene, α, α′-di-n-butoxy-p-xylene, α, α′-di-sec-butoxy-p-xylene, α, α′-diisobutoxy-p-xylene and the like. .

In the reaction of the present invention, 1 to 5 mol, preferably 1.1 to 3 mol of a dihydroxy compound is added to 1 mol of the xylylene compound represented by the general formula (II), and the mixture is heated in the presence of an acid catalyst. Do it. The reaction temperature is 11
The reaction temperature is desirably 0 ° C or higher, and at 110 ° C or lower, the reaction becomes extremely slow. In order to shorten the reaction time as much as possible, the reaction temperature is desirably in the range of 130 to 250C, and more desirably in the range of 130 to 180C. The reaction time is about 1 to 30 hours. As the acid catalyst, an inorganic or organic acid, for example, a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, an organic sulfonic acid such as p-toluenesulfonic acid, further zinc chloride, aluminum chloride, stannic chloride, Friedel-Crafts-type catalysts such as ferric chloride, sulfates such as dimethyl sulfate and diethyl sulfate, 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
001 to 10% by weight, preferably 0.001 to 1% by weight
It is about.

When R is a halogen in the xylylene compound of the general formula (II), a method of reacting with an alkali metal salt of a dihydroxy compound to form a benzyl ether type and transferring the benzyl ether type with an acid catalyst is also possible. When employing such a method, the reaction temperature can be set lower than the Friedel-Crafts reaction. That is, both the benzyl etherification reaction and the transfer reaction proceed when the temperature is 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. In addition, in the reaction of reacting the alkali metal salt of the dihydroxy compound with the xylylene compound, it is usually preferable to react in a water-immiscible solvent such as benzene, toluene, and chlorobenzene with a two-layer system of water,
After the reaction, it can be transferred to the next transfer reaction by a treatment such as liquid separation and washing with water.

In addition to the above method for producing the phenolic polymer of the present invention, the reaction is usually carried out without a solvent, but a solvent inert to the reaction may be used. These solvents include, for example, 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 hydrocarbons such as toluene and xylene. Hydrogens, 1,
2-dichloroethane, 1,1,2-trichloroethane,
Examples include halogenated hydrocarbons such as monochlorobenzene, and aprotic polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. The amount of these solvents to be used is appropriately selected from a small amount to suspend the reaction raw material system to an amount sufficient to uniformly dissolve the reaction raw material system. However, usually, the solvent may be in a range of 10 wt% to 300 wt% of all the raw materials.

The reaction may be carried out in any manner, such as a method in which the raw materials are charged all at once and a reaction is performed, or a method in which a xylylene compound is added to a mixture of a dihydroxy compound or the like and a catalyst and the reaction is sequentially performed. Selected. Hydrogen halide, water or alcohol generated as the reaction proceeds is trapped and removed out of the system. After the reaction is completed, the volatile components are removed, the mixture is discharged as it is, and the mixture is cooled to obtain a hard and brittle phenol polymer of the present invention. The resin from which the unreacted dihydroxy compound has been removed by means such as vacuum distillation or extraction with an aqueous alkaline solution and washing with water before discharging is also a phenolic polymer of the present invention. The phenolic polymer of the present invention thus obtained has an average molecular weight in the range of 300 to 10,000 and a softening point (JIS-K-2548).
(Based on a ring and ball softening point measuring apparatus). In addition, when it is required to reduce the amount of the unreacted dihydroxy compound in the curing agent of the epoxy resin, the content of the remaining unreacted dihydroxy compound is preferably 5% by weight or less.

Next, an epoxy resin composition using such a phenolic 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 novolak epoxy resin, o-cresol novolak epoxy resin and the like. Epoxidized novolak resin of phenols and aldehydes, epoxidized aralkyl resin by xylylene bond such as phenol, naphthol, epoxidized phenol dicyclopentadiene resin, bisphenol A, bisphenol F, bisphenol S, biphenol, substitution Glycidyl ester type epoxy resin obtained by reaction of epichlorohydrin with diglycidyl ethers such as biphenol and dihydroxynaphthalene, and polybasic acids such as phthalic acid and dimer acid, diaminodiphenylmethane, diamido 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 phenol polymer is used as a curing agent for these epoxy resins. In this case, a widely used compound other than the phenolic polymer of the present invention may be used in combination as the curing agent. These are, for example,
Phenol, cresol, xylenol, resorcinol,
Novolak-type phenolic resins obtained by subjecting phenols such as catechol, bisphenol A, bisphenol F and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde to a condensation reaction in the presence of an acidic catalyst, and aralkyl resins by xylylene bonds such as phenol and naphthol Phenol dicyclopentadiene resin, and these may be used alone or in combination of two or more. The equivalent ratio with the epoxy resin is not particularly limited, but is 0.5 to 1.
5 is preferred.

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 fibrous bodies such as glass fibers and carbon fibers. Among these, crystalline silica and / or fusible silica are preferred from the viewpoint of the coefficient of thermal expansion and the thermal conductivity. Further, considering the fluidity during molding of the resin composition, the shape is preferably spherical, or a mixture of spherical and irregular. The blending amount of the inorganic filler is 100% based on the total weight of the epoxy resin and the curing agent.
９００900% by weight, preferably 2
It is 00 to 600% by weight.

In the present invention, it is desirable to add various additives in view 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 a coupling agent include silane-based, titanate-based, aluminate-based and zircoaluminate-based coupling agents. Agents can be used. Among them, a silane coupling agent is preferable, and a silane coupling agent having a functional group that reacts with an epoxy resin is particularly preferable. Examples of such a silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, and 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 the like, and these can be used alone or in combination. It is preferable that these silane coupling agents are previously fixed to the surface of the inorganic filler by adsorption or reaction.

In the present invention, in curing the resin composition, it is desirable to use a curing accelerator.
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; and organic phosphines such as tributylphosphine, triphenylphosphine and tolylphosphine. ,
Tetraphenylphosphonium tetraphenylborate,
There are tetraphenylborons such as triethylammonium tetraphenylborate, 1,8-diaza-bicyclo (5,4,0) undecene-7 and derivatives thereof. The above-mentioned curing accelerators may be used alone or in combination of two or more, and the combination of these curing accelerators is 0.01 to 100 parts by weight based on the total amount of the epoxy resin and the curing agent. Used in the range of 10 parts by weight.

In addition to the above components, the resin composition of the present invention may contain, if necessary, a release agent such as a fatty acid, a fatty acid salt, and a wax, a flame retardant such as a bromo compound, antimony, and phosphorus;
A molding material can be obtained by blending a colorant such as carbon black, various silicone oils and the like, mixing and kneading.

Next, a molding composition containing the phenolic polymer of the present invention and hexamethylenetetramine will be described. These contain the phenolic polymer of the present invention as an essential component, and if necessary, may be used in combination with another phenolic resin. For this phenolic polymer, hexamethylenetetramine, and if necessary, an inorganic filler or wood powder. , A curing accelerator, a pigment, a lubricant, a rust inhibitor, 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,
Bisphenol A, phenols such as bisphenol F, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde novolak phenol resin obtained by a condensation reaction under an acidic catalyst, phenol, aralkyl resin by xylylene bond such as naphthol, There are phenol dicyclopentadiene resins and the like, which may be used alone or in combination of two or more.

In the molding material composition of the present invention, an inorganic filler, wood powder, and a curing accelerator may be used. As this inorganic filler, for example, asbestos, mica, glass fiber,
Examples thereof include carbon fiber, silica, alumina, calcium carbonate, and magnesium oxide, 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 flour to the resin component is usually 0.3 to 4: 1 by weight. The amount of the organic acid used as the curing accelerator is 0.02 to hexamine.
The weight ratio is 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 composition for a molding material of the present invention, based on each of the above components,
It can be compounded and kneaded at 120 ° C. by a roll mill to obtain a molding material.

[0024]

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 In a reactor, 1090 g (5 mol) of 4,4′-thiodiphenol, 415 g of α, α′-dimethoxy-p-xylene
(2.5 mol) was charged and dissolved by heating. Internal temperature 130
At 0 ° C., 1.5 g of the catalytic methanesulfonic acid were added with stirring. Slowly raise the temperature to 8 at the internal temperature of 155 to 160 ° C.
Aged for hours. On the way, generated methanol was distilled out of the system. After aging, volatiles were removed under reduced pressure of an aspirator and immediately discharged to a porcelain dish. Yield 1220
g. The resulting 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 5 In Synthesis Example 1, the types of the dihydroxy compound and the xylylene compound were changed as shown in Table 1 (Table 1).
To give a phenolic polymer. The results are shown in Table 1.

[0026]

[Table 1]

[0027]

[0028]

Examples 1-4 With respect to the phenolic polymers produced in Synthesis Examples 1 and 5, o-cresol novolak type epoxy resin (EOCN-102S; manufactured by Nippon Kayaku) was used as an epoxy resin.
Diglycidyl ether of 1,6-dihydroxynaphthalene (Epiclon EXA-4032; manufactured by Dainippon Ink and Chemicals), 4,4′-dihydroxy-3,3 ′, 5,5′-
Diglycidyl ether of tetramethylbiphenyl (YX
-4000H; manufactured by Yuka Shell Epoxy) and the like in the ratio shown in Table 2 (Table 2), and physical properties of a cured product obtained by casting the mixture were measured. The test piece for measuring physical properties was transfer molded (180 ° C., 30 kg / cm ² , 3
min). The results are shown in Table 2.

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

[0031]

[Table 2]

Examples 5 to 8 and Comparative Example 2 Various fillers were added to the epoxy resin compositions of Examples 1 to 4 and Comparative Example 1 in the proportions shown in Table 3 and cast and cured in the same manner. A product was obtained and the physical properties of the product were measured. Using a mixture of the same composition, a test element (10 mm × 10 mm square) was mounted on the element mounting portion of a flat package type semiconductor device lead frame, and then transfer molding (180 ° C., 30 kg / cm ² , 3 min) to obtain a test semiconductor device. A VPS test (crack generation test) was performed using this test semiconductor device. The results are shown in Table 3 (Table 3).

[0033]

[Table 3]

The symbols, substances and measuring methods used in Tables 2, 3 and 4 are shown below. -EOCN-102S; o-cresol novolac type epoxy resin (Nippon Kayaku) Epoxy equivalent 214 g / e
q BRG # 558; phenol novolak resin (manufactured by Showa Kobunshi) OH value 104 g / eq phenol dicyclopentadiene resin; manufactured by Mitsui Toatsu Chemicals (DPR-5000) represented by general formula (3) Phenol resin, average molecular weight 530, OH value 173
g / eq

[0035]

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

[0036]

Embedded image ・ Naphthol ziloc resin; Mitsui Toatsu Chemical (α-N
X) A naphthol resin represented by the general formula (5), having an average molecular weight of 640 and an OH value of 220 g / eq.

[0037]

Embedded image

C11Z; undecyl imidazole (manufactured by Shikoku Fine Chemical) inorganic filler; spherical fused silica (Halimic S-CO
Mixture of 50 parts by weight of Micron Corporation and 50 parts by weight of amorphous fused silica (Hughes Rex RD-8, manufactured by Tatsumori Co., Ltd.) Silane coupling agent; (SZ-6083, manufactured by Toray Dow Corning Silicone Silicone) -Glass transition temperature; TMA method (measured by TMA-System DT-30, Shimadzu)-Flexural strength, elastic modulus: JIS K-6911-Boiling water absorption; Measured for weight increase after boiling in 100 ° C boiling water for 2 hours. V. P. S test: The test semiconductor device was set at 65 ° C.
Immediately after standing for 168 hours in a 95% constant temperature and humidity chamber, a 215 ° C. Freonate solution (manufactured by Sumitomo 3M, FC
-70), and the number of semiconductors having cracks in the package resin was counted. The test value is indicated by a fraction, the numerator is the number of semiconductor devices having cracks, and the denominator is the number of semiconductor devices subjected to the test.

Example 9, Comparative Examples 3 to 5 The phenolic polymer obtained in Synthesis Example 1, and phenol novolak resin # 2000 (manufactured by Showa Polymer) and phenol ziloc resin (manufactured by Mitsui Toatsu Chemical; Millex 225, average molecular weight 2400), phenol dicyclopentadiene resin (Mitsui Toatsu Chemicals; DPR-3)
000, average molecular weight 720), and hexamethylenetetramine was added at the ratio shown in Table 4 and roll-kneaded at 120 ° C. for 5 minutes to obtain a molding material composition. These compositions were compression molded at 190 ° C. for 5 minutes to obtain test pieces for evaluating physical properties. Except for the hardness measurement, post-curing was performed under the following conditions, and the test was performed. The results are shown in Table 4.・ Post cure condition 170 ℃ / 16hr + 220 ℃ / 4
hr + 250 ° C / 4hr

[0040]

[Table 4]

[0041]

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-56-98229 (JP, A) JP-A-47-14300 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/62 C08G 61/02 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A dihydric compound represented by the general formula (I)
Proxy compound [Formula 1] (Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl having 1 to 9 carbon atoms)
X represents a cycloalkyl group or an aryl group, and X represents
-S-, -O-, an alkylene group having 5 to 10 carbon atoms or
A cycloalkylene group) and the general formula (II)
Xylylene compound embedded image represented (In the formula, R is a halogen atom, a hydroxyl group, or a group having 1 to 4 carbon atoms.
Of the compound (I) / (I
When the molar ratio of I) is in the range of 5/1 to 1/1, the presence of an acid catalyst
Average molecular weight of 300 to 100 obtained by condensation reaction below
00, a phenolic polymer having a softening point of 50 to 160 ° C. 2. A composition containing a polyfunctional epoxy compound and a curing agent.
2. The resin composition according to claim 1, wherein the curing agent is
Epoxy resin composition characterized by being a polyester polymer
object. 3. A polyfunctional epoxy compound, a curing agent, and an inorganic filler.
In a resin composition containing a filler, a curing agent is claimed.
An epoch characterized by being the phenolic polymer according to (1).
Xy resin composition. 4. A phenolic polymer, hexamethylene tet
In a composition containing lamin, the phenolic polymer is
A phenolic polymer according to claim 1.
Molding composition.